Foam compositions comprising silicone MQ resins and related articles and methods

Abstract

A foam composition comprising a vehicle having voids therein and a silicone MQ resin. The vehicle includes at least one of a silicone-free organic polymer or organic monomer. The foam composition comprises no more than 50% by weight of water. Articles including the foam compositions and methods for making the foam compositions and articles are also described.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 348,396, filed on June 2, 2022, the disclosure of which is incorporated herein by reference in its entirety. Background Art

[0003] In foam, gas bubbles are separated from each other by a thin liquid film. Typically, surfactants work by reducing the surface tension of the liquid so that bubbles introduced below the surface of the liquid can be retained in the liquid. Surfactants can also stabilize foam by adsorbing at the interface of the bubbles and the liquid film and providing a barrier to bubble coalescence. Forming foam in organic liquids is generally more challenging than forming aqueous foams. Some fluorinated surfactants are known to produce stable foams in organic liquids. However, there has been an industry trend recently to avoid the use of fluorinated surfactants.

[0004] In U.S. Pat. No. 4,415,615 (Esmay et al.), certain silicone surfactants have been reported to be useful for foaming organic liquids. On the other hand, silicone MQ resins have been reported to be defoaming agents in U.S. Pat. No. 6,207,722 (Juen et al.) and in the handbook "Your Technology - Siltech Chemistry" published in August 2016 by Siltech Corporation of Toronto, Canada.

[0005] Many foam compositions contain inorganic particles for a variety of reasons. Some of these particles are used as nucleating agents. Other particles act as fillers to change the physical properties of the composition, such as changing the rheological properties of the composition. It has been found that other particles (e.g., hydrophobic fumed silica) can be used as defoamers. Fumed silica, also known as pyrogenic silica, consists of primary particles that are irreversibly bonded together in the form of aggregates with an average size of 200nm to 300nm. 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

[0006] We now report that compositions comprising silicone MQ resins are capable of forming persistent foam in organic liquids. Compositions comprising silicone MQ resins are surprisingly capable of forming persistent foam, even though silicone MQ resins have been reported to be defoamers. In some embodiments, compositions comprising silicone MQ resins and polyoxyalkylene-modified polydimethylsiloxanes or alkoxylated alcohols are surprisingly more capable of forming persistent foam than compositions comprising only polyoxyalkylene-modified polydimethylsiloxanes or alkoxylated alcohols, even though polyoxyalkylene-modified polydimethylsiloxanes and alkoxylated alcohols are reported to be useful as surfactants.

[0007] In one aspect, the present disclosure provides a foam composition comprising a vehicle having voids therein 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 no more than 50 wt % water.

[0008] In another aspect, the present disclosure provides an adhesive tape (eg, a pressure-sensitive adhesive tape) comprising the above-described foam composition.

[0009] In another aspect, the present disclosure provides an article comprising the foam composition described above. The article may be, for example, a gasket or an automotive body molding.

[0010] In another aspect, the present disclosure provides a method for making the above-mentioned foam composition, the method comprising introducing a blowing agent into a composition comprising a vehicle and a silicone MQ resin to form voids in the composition.

[0011] In another aspect, the present disclosure provides a method of making a tape, wherein the method comprises foaming an adhesive composition comprising a silicone MQ resin and a vehicle comprising at least one of a non-silicone-containing organic polymer or an organic monomer, and subsequently applying the composition to a substrate.

[0012] As used in this article:

[0013] In the present application, terms such as "one", "a kind of" and "the / said" are not intended to refer to only a single entity, but rather to general categories that include specific examples that can be used for illustration. The terms "one", "a kind of", "the" and "said" can be used interchangeably with the term "at least one (kind)". The phrases "at least one (kind) of..." and "comprising at least one (kind) of..." followed by a list refer to any one of the items in the list and any combination of two or more items in the list. Unless otherwise indicated, all numerical ranges include their end values ​​and non-integer values ​​between the end values ​​(e.g., 1 to 5, including 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5).

[0014] The term "acrylic" refers to acrylic and methacrylic polymers, oligomers, and monomers.

[0015] The term "(meth)acrylate" with respect to a monomer, oligomer or polymer means a vinyl functional alkyl ester formed as the reaction product of an alcohol and acrylic acid or methacrylic acid. "(Meth)acrylate" individually and collectively includes methacrylates and acrylates.

[0016] Unless otherwise indicated, "alkyl group" and the prefix "alk-" include both straight-chain and branched-chain groups having up to 30 carbon atoms (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbon atoms).

[0017] "Alkylidene" is a polyvalent (eg, divalent or trivalent) form of an "alkyl" group as defined above.

[0018] "Arylalkylene" refers to an "alkylene" portion to which an aryl group is attached.

[0019] As used herein, "aryl" and "arylene" include carbocyclic aromatic rings or ring systems, for example, having 1, 2 or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring, which ring is optionally substituted with up to five substituents, including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy groups having up to 4 carbon atoms, halogen (i.e., fluorine, chlorine, bromine or iodine), hydroxyl, or nitro groups, examples of which include phenyl, naphthyl, biphenyl, fluorenyl, as well as furanyl, thienyl, pyridyl, quinolyl, isoquinolyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl and thiazolyl.

[0020] The term "polymer" refers to a molecule having a structure comprising multiple repeating units derived actually or conceptually from one or more monomers. The term "monomer" refers to a molecule of low relative molecular mass that can be combined with other molecules to form a polymer. The term "polymer" includes homopolymers and copolymers and homopolymers or copolymers that can be formed in a miscible blend, for example by coextrusion or by reaction. The term "polymer" includes random polymers, block polymers, graft polymers and star polymers. The term "polymer" includes oligomers.

[0021] A "unit" of a polymer or oligomer is a segment of the polymer or oligomer derived from a single monomer.

[0022] The term "crosslinking" refers to the joining together of polymer chains by covalent chemical bonds (usually via crosslinking of molecules or groups) to form a network polymer. Crosslinked polymers are generally characterized by insolubility, but may be swellable in the presence of appropriate solvents. The term "crosslinked" includes partially crosslinked. Thermosetting polymers are crosslinked.

[0023] The term "persistent foam" means that gas voids are present in the composition for a period of at least five minutes after the composition is foamed.

[0024] The term "hydrocarbon" refers to a compound having only carbon and hydrogen atoms. With respect to hydrocarbon alcohols or hydrocarbon surfactants, the descriptor "hydrocarbon" excludes the hydroxyl group or hydrophilic group of the surfactant.

[0025] The term "ceramic" refers to glasses, crystalline ceramics, glass-ceramics, and combinations thereof.

[0026] The above summary of the present disclosure is not intended to describe each disclosed embodiment or each implementation of the present disclosure. The following description illustrates exemplary embodiments in more detail. Therefore, it should be understood that the drawings and the following description are only for illustrative purposes and should not be construed as undue limitations on the scope of the present disclosure. DETAILED DESCRIPTION

[0027] The foam composition of the present disclosure and / or the foam composition that can be used in the method of the present disclosure comprises a silicone MQ resin. The silicone MQ resin is an organic silicon polymer made of structural units called M units and Q units, wherein the M unit is composed of the formula (R)3SiO 1 / 2 Indicates that the Q unit is composed of the formula SiO 4 / 2 , wherein Si is silicon, O is oxygen, and R is hydrogen or an aliphatic organic group or an aromatic organic group. Therefore, the silicone MQ resin contains silicon atoms bonded to one oxygen atom and silicon atoms bonded to four oxygen atoms. The representative structure of the silicone MQ resin is shown in Formula I below.

[0028]

[0029] Suitable R substituents include hydrogen, alkyl, aryl or alkylene groups subjected to at least one operation of being inserted or end-capped by aryl or heterocyclic groups, wherein alkyl and the alkylene groups subjected to at least one operation of being inserted or end-capped by aryl or heterocyclic groups are not substituted or substituted by halogen and are optionally inserted by at least one chain -O-, -NH-, -N (alkyl)-, -S-, -Si- or a combination thereof, and wherein aryl, aryl and heterocyclic groups are not substituted or substituted by at least one alkyl, alkoxy, halogen or a combination thereof. R groups can be selected independently of one another. In some embodiments, each R group is the same. In some embodiments, R is not fluorinated. In some embodiments, R is not halogenated. In some embodiments, R is not hydrogen. In some embodiments, each R is independently hydrogen, alkyl, aryl or alkylene groups subjected to at least one operation of being inserted or end-capped by aryl groups in at least one chain -O- groups or aryl groups. Suitable alkyl groups for R typically have 1 to 20, 1 to 18, 1 to 12, 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Examples of useful alkyl groups include methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, and octadecyl. In some embodiments, each R is independently an alkyl group having up to 18 (in some embodiments, up to 4, 3, or 2) carbon atoms, phenyl, benzyl, or C6H5C2H4-. In some embodiments, each R is independently methyl, phenyl, C6F4- ... 13 In some embodiments, each R is independently alkyl. In some embodiments, each R is independently methyl or phenyl. In some embodiments, each R is methyl; in these embodiments, the silicone MQ resin comprises methyl groups. In some embodiments, the silicone MQ resin is non-fluorinated. In some embodiments, the silicone MQ resin is non-halogenated.

[0030] The ratio of M units to Q units affects the properties of silicone MQ resins. Silicone MQ resins with an M:Q ratio greater than 1 are generally liquid at room temperature. Silicone MQ resins with an M:Q ratio of 1 or less are generally solid at room temperature. As used herein, "room temperature" refers to 20°C to 25°C. In some embodiments, the M:Q ratio of silicone MQ resins is 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 M:Q ratio of silicone MQ resins is 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 no greater than 3: 1, and in some embodiments, no greater than 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. For purposes of this disclosure, the M:Q ratio is determined by NMR spectroscopy using the method described in the following examples.

[0031] can be obtained by one or more of the formula (R)3-Si-R 1 A compound represented by and one or more compounds represented by formula (R 1 )4Si is reacted to prepare a silicone MQ resin, wherein R is as defined above in any of its embodiments, and R 1 The term "hydrolyzable group" refers to a group that can react with water under atmospheric pressure. The reaction with water can be optionally catalyzed by an acid or a base. Suitable hydrolyzable groups include halogens (e.g., iodine, bromine, chlorine); alkoxy (e.g., -O-alkyl), aryloxy (e.g., -O-aryl), acyloxy (e.g., -OC(O)-alkyl), amino (e.g., -N(R A )(R B ), polyalkyleneoxy; and oxime (e.g., -ON=C-(R A )(R B ), where 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. 1 is independently chlorine or an alkoxy group having up to 12 (or up to 6 or 4) carbon atoms. 1 are independently methoxy or ethoxy. 1 and (R 1 )4Si compound reaction, during the hydrolysis period R 1The Si-OH groups react with each other to form silicone-oxygen bonds. The hydrolysis and condensation can be carried out by conventional methods, for example by heating a mixture of the formula R-Si (R) in water (optionally in the presence of an acid or base). 1 )3 and optionally R 2 -Si(R 1 )3 compound.

[0032] After hydrolysis and condensation, typically -OH groups are present in the silicone MQ resin. The -OH groups can be further reacted with a capping agent to convert the hydrolyzed groups, e.g., -OH, into -OSi(R)3. Suitable capping agents include those having the formula R 1 -Si(R)3 and O[Si(R)3]2 end-capping agent, where R 1 For example, as defined above in any embodiment in its embodiment. Suitable end-capping agents also include end-capping agents with formula H-Si (R) 3, which can react with hydroxyl groups in the presence of transition metal catalysts (e.g., palladium catalysts and platinum catalysts). Silicone MQ resins contain additional groups with formula -Si (R) 3 after end-capping, wherein R is defined above in any embodiment in its embodiment, independent of other R groups in silicone MQ resin. In some embodiments, the hydroxyl content of silicone MQ resin is in the range of 185 milliequivalents / kg to 1840 milliequivalents / kg (meq / kg). In some embodiments, the hydroxyl content of silicone MQ resin is in the range of 500 milliequivalents / kg to 1000 milliequivalents / kg (meq / kg). For the purpose of this disclosure, the method for determining the MQ ratio described in the following examples is used to determine the hydroxyl content by NMR spectroscopy.

[0033] Depending on the M:Q stoichiometry, synthetic preparation and end-capping, silicone MQ resins can adopt a variety of polycyclic structures and have a variety of properties, including solubility in organic vehicles. Although Formula I is shown as having an organized structure at least in the central portion, it should be understood that silicone MQ resins can have a more random structure. Therefore, silicone MQ resins that can be used to practice the present disclosure include three-dimensional and branched random copolymers.

[0034] Silicone MQ resins are available from a variety of commercial sources, for example, from Siltech, Toronto, Ontario, Canada, under the trade designation "SILMER Q", from Dow Chemical Company, Midland, Michigan, under the trade designation "DOWSIL", from Wacker Chemie, Munich, Germany, from Momentive Performance Materials, Waterford, New York, under the trade designation "SILGRIP", from BYK-Chemie, Wesel, Germany, and from Gelest, Inc., Morrisville, Pennsylvania. Silicone MQ resins have been reported to provide release properties, lubricity, tack, softness, and / or repellency. In addition, MQ resins are explicitly reported as "defoamers" and "antifoaming agents". Silicone MQ resins are not generally referred to as surfactants. In some embodiments, silicone MQ resins do not contain alkoxy groups, such as those represented by the formula -(OR 2 ) n -OR 3 An alkoxy group represented by 2 and R 3 As defined below in any of their embodiments.

[0035] In some embodiments, the silicone MQ resin is present in the foam composition in a range of 0.1 wt % to 10 wt % based on the total weight of the foam composition. In some embodiments, the silicone MQ resin is present in the foam composition in a range of 0.1 wt % to 5 wt %, or in a range of 0.5 wt % to 3 wt %, 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 wt % and up to 10, 5, 4, or 3 wt %, based on the total weight of the foam composition.

[0036] In some embodiments, the foam composition of the present disclosure or the foam composition manufactured by the method of the present disclosure further comprises a nonionic surfactant. In some embodiments, the foam composition of the present disclosure or the foam composition manufactured by the method of the present disclosure further comprises a polyoxyalkylene-modified polydimethylsiloxane. Polydimethylsiloxane is an organosilicon polymer made of a structural unit called a D unit, which is a D unit of the formula (R)2SiO 2 / 2, wherein Si is silicon, O is oxygen, and R is a methyl group. In some embodiments, the polyoxyalkylene-modified polydimethylsiloxane is not fluorinated. In some embodiments, the polyoxyalkylene-modified polydimethylsiloxane is not halogenated. The polydimethylsiloxane comprises a repeating divalent unit represented by Formula II:

[0037] The polyoxyalkylene-modified polydimethylsiloxane further comprises a polyoxyalkylene-modified polydimethylsiloxane having the formula -Q-(OR 2 ) n -OR 3 The terminal unit represented by the formula III is a divalent unit:

[0038] or a combination thereof, wherein each Q is independently an alkylene group, an arylene group, and an alkylene group inserted or capped by an aryl group, one of which is optionally inserted or capped by at least one of the following groups: at least one ether (i.e., -O-), thioether (i.e., -S-), amine (i.e., -NR- 4 -), amide (i.e., -N(R 4 )-C(O)- or -C(O)-N(R 4 )-), esters (i.e., -OC(O)- or -C(O)-O-), thioesters (i.e., -SC(O)- or -C(O)-S-), carbonates (i.e., -OC(O)-O-), thiocarbonates (i.e., -SC(O)-O- or -OC(O)-S-), carbamates (i.e., -(R 4 )NC(O)-O-or-OC(O)-N(R 4 )-), thiocarbamate (i.e., -N(R 4 )-C(O)-S-or-SC(O)-N(R 4 )-), urea (ie, -(R 4 )NC(O)-N(R 4 )-), thiourea (i.e., -(R 4 )NC(S)-N(R 4 )). In the R 4 In any of these groups, R 4 is hydrogen, alkyl, aryl or arylalkylene, wherein aryl and arylalkylene are unsubstituted or substituted with at least one alkyl, alkoxy or combination thereof. 4 is hydrogen or alkyl, for example, an alkyl having 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl). 4is methyl or hydrogen. The phrase "interpolated by at least one functional group" refers to having a portion of an alkylene, arylalkylene or alkylarylene group on either side of the functional group. An example of an alkylene group interpolated by an ether is -CH2-CH2-O-CH2-CH2-. Similarly, an alkylene group interpolated by an arylene group has a portion of an alkylene group on either side of the arylene group (e.g., -CH2-CH2-C6H4-CH2-). In some embodiments, Q is an alkylene group having 1 to 10, 1 to 6, 1 to 4, 1 to 3 or 1 to 2 carbon atoms. For suitable polyoxyalkylene groups, each OR 2 are independently -OCH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2-, -OCH2CH(CH3)-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, -OCH2CH(CH2CH3)-, and -OC(CH3)2CH2-. In some embodiments, each OR 2 is independently -OCH2CH2-, -OCH(CH3)CH2- or -OCH2CH(CH3)-. In some embodiments, each OR 2 Each n is independently -OCH2CH2-. Each n is independently a value from 5 to 300 (in some embodiments, from 10 to about 250, or from 20 to about 200). For suitable polyoxyalkylene groups, each R 3 is hydrogen, alkyl, acyl, aryl or arylalkylene, wherein aryl and arylalkylene are unsubstituted or substituted with at least one alkyl, alkoxy or combination thereof. 3 R is hydrogen, alkyl, for example, alkyl having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or sec-butyl), or acyl having 2 to 4 carbon atoms (e.g., acetyl, propionyl, or butyryl). 3 is acetyl, methyl or hydrogen. In some embodiments, R 3 It is hydrogen or acetyl.

[0039] In some embodiments, the polyoxyalkylene-modified polydimethylsiloxane useful in the foam composition of the present disclosure may be represented by Formula IV:

[0040]

[0041] It may include or not include a 2 ) n -OR 3 represents the terminal unit, where each R 2 , R 3, Q and n are independently defined as above in any of their embodiments, and n'+m' is in the range of 10 to 500, 10 to 400, 10 to 300, 12 to 300, 13 to 300, 13 to 200, 10 to 100, 10 to 50 or 10 to 30. Such values ​​of n'+m' provide a polyoxyalkylene modified polydimethylsiloxane having a number average molecular weight of up to about 50,000 g / mole, 40,000 g / mole, 30,000 g / mole, 25,000 g / mole, 15,000 g / mole, 10,000 g / mole or 5,000 g / mole. Typically, the ratio of n' to m' is greater than 1:1 (in some embodiments, at least 2:1 or 3:1 or 5:1). In some embodiments, the number average molecular weight of the polyoxyalkylene modified polydimethylsiloxane as described herein in any embodiment of its embodiment is at least 750 g / mol, at least 900 g / mol or at least 1000 g / mol. In some embodiments, the number average molecular weight of the polyoxyalkylene modified polydimethylsiloxane as described herein in any embodiment of its embodiment is not more than 50,000 g / mol, 40,000 g / mol, 30,000 g / mol, 25,000 g / mol, 15,000 g / mol, 10,000 g / mol or 5,000 g / mol. The polysiloxane disclosed herein generally has a certain molecular weight distribution. Although formula IV is shown in block copolymers, it should be understood that the divalent units of formulas II and III can be positioned in copolymers without regulation. Therefore, the polysiloxanes that can be used to practice the present disclosure also include random copolymers.

[0042] 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 higher molecular weight materials, including number average molecular weights and weight average molecular weights) 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 purposes of this disclosure, the number average molecular weight of the polyoxyalkylene-modified polydimethylsiloxane is determined by NMR spectroscopy using the method described in the following examples.

[0043] In some embodiments, the foam composition of the present disclosure or the foam composition made by the method of the present disclosure further comprises an alkoxylated alcohol. In some embodiments, the alcohol has a straight or branched hydrocarbon chain containing 10 to 20 carbon atoms. Suitable alkoxylated alcohols include those of formula R 10 -(OR 2 ) n Alkoxylated alcohol represented by 2 and n are as described above in any of their embodiments, and R 10is a linear or branched alkyl or alkenyl chain having 10 to 20 carbon atoms. The alkoxylated alcohol may include at least one of polyoxyethylene (POE) and polyoxypropylene (POP) units in random or block form (i.e., wherein OR 2 alkyl ether, wherein the alkyl ether is independently -OCH2CH2-, -OCH(CH3)CH2- or -OCH2CH(CH3)-, and n is 1 to 100, 3 to 50 or 5 to 20). Suitable examples include POE (4 to 11) lauryl ether, POE (10 to 20) hexadecyl ether, POE (4 to 20) oleyl ether, POP (5) lauryl ether, POP (7) hexadecyl ether, POP (10) oleyl ether and POE (3) POP (5) lauryl ether, wherein the numerical values ​​in parentheses of POE and POP represent the number of units of oxyethylene units and oxypropylene units. In some embodiments, the alkoxylated alcohol is an alcohol ethoxylate. Suitable alkoxylated alcohols include pentamolar ethoxylates of straight chain, primary carbon number 12-14 alcohols available, for example, under the trade name "SURFONIC L24-5" surfactant from Huntsman Corporation, The Woodlands, Tex., and alcohol ethoxylates available, for example, under the trade name "ECOSURFEH-6" from Dow Chemical Company. In some embodiments, the alkoxylated (e.g., ethoxylated, propoxylated, or a combination thereof) alcohol is an alkoxylated branched alcohol, and in some embodiments, an alkoxylated Guerbet alcohol. 10 Examples of Guerbet alcohols are represented by the formula: Suitable alkoxylated Guerbet alcohols include those available under the trade designation "LUTENSOL XXP" from BASF Corporation, Florham Park, NJ.

[0044] In some embodiments, at least one of the silicone MQ resin and the polyoxyalkylene-modified polydimethylsiloxane or alkoxylated alcohol is present in the foam composition in a combined amount of 0.1 wt % to 10 wt % based on the total weight of the foam composition. In some embodiments, at least one of the silicone MQ resin and the polyoxyalkylene-modified polydimethylsiloxane or alkoxylated alcohol is present in the foam composition in a combined amount of 0.1 wt % to 5 wt %, or 0.5 wt % to 3 wt % based on the total weight of the foam composition. At least one of the silicone MQ resin and the polyoxyalkylene-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 wt % and up to 10, 5, 4, or 3 wt % based on the total weight of the foam composition. In some embodiments, the foam composition does not contain a fluorinated surfactant.

[0045] The foam composition of the present disclosure and / or the foam composition that can be used for the method of the present disclosure include a medium having voids therein. The medium includes at least one of an organic polymer or an organic monomer that does not contain silicone. In some embodiments, the medium includes an organic polymer and an organic monomer for making the organic polymer. The voids may be present at the surface of the composition, dispersed throughout the composition, or a combination of these two situations. For some applications, the voids are uniformly dispersed throughout the composition. The voids typically include at least one gas; therefore, these voids may be referred to as gas voids or bubbles. In some embodiments, the foam composition includes a microporous structure in which the voids are in the form of closed cells. In some embodiments, the foam composition is an open-cell foam.

[0046] The vehicle of the foam composition of the present disclosure or the vehicle manufactured by a method in the method of the present disclosure can include multiple components, and can be in the form of solid, liquid or their combination. The vehicle can be selected based on the desired characteristic (for example, viscosity, rigidity, hardness, density, volume, transparency, flexibility, conformability, resilience, creep, strength, modulus, elongation, chemical resistance, temperature resistance, environmental resistance and compressibility) of the foam composition. In some embodiments, when foaming, the vehicle is a liquid, and can be, for example, a solution, an emulsion, a suspension, a dispersion, a slurry or a melt. In some embodiments, the vehicle includes an organic liquid. The available example of an organic liquid includes acid, alcohol, ketone, aldehyde, amine, ether, hydrocarbon, halogenated hydrocarbon, monomer, oligomer and polymer.

[0047] In some embodiments, the vehicle includes water. In some embodiments, the vehicle excludes water. The foam composition comprises no more than 50%, 40%, 30%, 20%, 10%, 5%, or 1% by weight water.

[0048] Examples of useful organic vehicles include organic polymers. Suitable organic polymers for use in the vehicle include natural rubber resins and synthetic rubber resins, including thermosettable rubbers and thermoplastic rubbers and elastomers, such as nitrile rubber (e.g., acrylonitrile butadiene), polyisoprene rubber, polychloroprene rubber, polybutadiene rubber, butyl rubber, ethylene-propylene-diene monomer rubber (EPDM), Polypropylene-EPDM elastomers, ethylene-propylene rubbers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-butadiene-styrene rubbers, styrene-isoprene-styrene rubbers, styrene-ethylene-butylene-styrene rubbers, styrene-ethylene-propylene-styrene rubbers, polyisobutylene rubbers, ethylene vinyl acetate rubbers, polymethacrylate rubbers, polyacrylate rubbers (e.g., copolymers of isooctyl acrylate and acrylic acid or any of those described in further detail below), polyesters, polyetheresters, polyvinyl ethers, polyurethanes, and blends and copolymers thereof. Useful copolymers include linear block copolymers, radial block copolymers, star block copolymers, and tapered block copolymers, and combinations thereof.

[0049] Other elastomers suitable for use in the vehicle include fluoroelastomers (eg, polytrifluoroethylene, polyvinylidene fluoride, hexafluoropropylene, and fluorinated ethylene-propylene copolymers), fluorosilicones, and chloroelastomers (eg, chlorinated polyethylene), and combinations thereof.

[0050] Additional examples of organic polymers suitable for use in the vehicle include thermoplastic resins such as polyacrylonitrile, acrylonitrile butadiene styrene, styrene acrylonitrile, cellulose, chlorinated polyethers, vinyl ethylene acetate, fluorocarbons (e.g., polychlorotrifluoroethylene, polytetrafluoroethylene, fluorinated ethylene-propylene, and polyvinylidene fluoride), polyamides (e.g., polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyundecanamide, polylauramide, and polyacrylamide), polyimides (e.g., polyetherimide), polycarbonates, polyolefins (e.g., polyethylene, polypropylene, polybutylene, and poly-4-methylpentene), polyalkylene terephthalates (e.g., polyethylene terephthalate), polyoxyalkylene oxides (e.g., polyphenylene oxide), polystyrene, polyurethanes, polyisocyanurates, vinyl polymers (e.g., polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyvinylidene chloride), and combinations thereof.

[0051] Additional examples of organic polymers suitable for use in the vehicle include thermosettable resins such as polyesters and polyurethanes and mixtures and copolymers thereof, 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 urethanes, acrylated polyesters, acrylated acrylics, acrylated polyethers, and acrylated oils), alkyd resins (such as urethane alkyds, polyester resins, reactive urethane resins), phenolic resins (e.g., resols, novolacs, and phenol-formaldehyde resins), phenolic / latex resins, epoxy resins (e.g., bisphenol epoxy resins, aliphatic and cycloaliphatic epoxy resins, epoxy / urethane resins, epoxy / acrylate resins), isocyanate resins, isocyanurate resins, reactive vinyl resins, and mixtures thereof.

[0052] In some embodiments, the vehicle comprises at least one of isocyanate, polyurethane or polyurea. Various isocyanates and polyols and polyurethanes made therefrom can be used in the foam composition of the present disclosure. In some embodiments, the foam composition is polyurethane foam, and the method for making the foam composition is a method for making polyurethane foam.

[0053] 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.

[0054] In some embodiments, the medium includes adhesive compositions, such as pressure-sensitive adhesive compositions, hot melt adhesive compositions, thermosetting adhesive compositions and thermoplastic adhesive compositions. The medium may include any pressure-sensitive adhesive compositions, including solvent-coated, hot melt-coated, radiation-curable (e.g., with electron beams, actinic radiation such as visible light and UV and heat) and combinations thereof. Pressure-sensitive adhesive (PSA) compositions suitable for medium include tackified rubber adhesives (e.g., natural rubber, olefins, polyisoprene, polybutadiene, polyurethane, styrene-isoprene-styrene and styrene-butadiene-styrene block copolymers and other elastomers), and tackified and non-tackified acrylic adhesive compositions. In some embodiments, the PSA composition is not and / or does not include silicone rubber.

[0055] In some embodiments, the vehicle includes at least one of an acrylic polymer (e.g., an acrylic PSA) or a precursor thereof (e.g., a first acrylic monomer and an optional second acrylic monomer). In some embodiments, the vehicle includes a copolymer of an alkyl ester of acrylic acid as a first monomer and an optional minor portion of a second monomer. Useful acrylates include acrylates or methacrylates of monohydric alcohols having 1 to 20 carbon atoms. Suitable acrylates or methacrylates of monohydric alcohols include esters represented by Formula V:

[0056] CH2=C(R 5 )COOR 6 (V)

[0057] Where R 5 is hydrogen or a methyl group, and R 6 is 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, which alkyl group may be linear, branched, cyclic or polycyclic. Examples of suitable monomers represented by Formula V include n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, isopentyl 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 foregoing acrylates, and combinations thereof. Further examples of suitable monomers for the vehicle include mixtures of at least two or at least three structural isomers of secondary alkyl (meth)acrylates of formula (VI):

[0058]

[0059] Where R 7 and R 8 Each independently is C1 to C 30 Saturated straight chain alkyl group; R 7 and R 8 The sum of the number of carbon atoms in is 7 to 31; and R 5 is hydrogen or a methyl group. In some embodiments, R 7 and R 8The sum of the number of carbons in 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 US Pat. No. 9,102,774 (Clapper et al.).

[0060] The second monomer unit may be more polar than the first monomer unit. Examples of suitable second monomers that can be used to prepare acrylic PSAs include acrylic acid (e.g., acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid), acrylamide (e.g., acrylamide, methacrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, N-octylacrylamide, N-tert-butylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-ethyl-N-dihydroxyethylacrylamide, and methacrylamides of the foregoing acrylamides), hydroxy 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, tert-butyl acrylate,

[0063] The invention also includes but is not limited to methylaminoethyl ester, aminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate and methacrylates of the foregoing acrylates), N-vinyl pyrrolidone, N-vinyl caprolactam, α-olefins, vinyl ethers, vinyl esters (vinyl acetate, vinyl benzoate, vinyl 4-tert-butylbenzoate, vinyl cinnamate, vinyl decanoate, vinyl neodecanoate, vinyl neononanoate, vinyl neopentanoate, vinyl propionate, vinyl stearate and vinyl valerate), allyl ethers, styrene 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 a second monomer unit of at least one of acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, N-substituted acrylamide, N,N-disubstituted acrylamide, hydroxyalkyl acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, 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.

[0061] Crosslinked acrylic PSA can be manufactured, for example, by incorporating one or more multifunctional crosslinking monomers into the formulation. Suitable multifunctional monomers include diacrylic acid esters of glycols, such as ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, butane diol diacrylate, butane-1,3-diyl diacrylate, pentanediol diacrylate, hexanediol diacrylate (including 1,6-hexanediol diacrylate), heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate and the dimethacrylate of any of the aforementioned diacrylates. Further suitable multifunctional monomers include polyacrylates of polyols, such as glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol tetraacrylate, and combinations thereof. Further suitable multifunctional crosslinking monomers include multifunctional acrylate oligomers comprising two or more acrylate groups. The multifunctional acrylate oligomer can be a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, a polyacrylic acid acrylate, a methacrylate of any of the foregoing acrylates, or a combination thereof. Crosslinking can be achieved in the absence of a crosslinking agent by using high energy radiation such as gamma or electron beam radiation.

[0062] Typically, acrylic acid alkyl esters (e.g., the first monomer represented by formula V or VI) are used in an amount of 75% to 100% by weight based on the total weight of the monomer for the manufacture of acrylic polymers, and the second monomer as described above is used in an amount of 0% to 25% by weight based on the total weight of the monomer for the manufacture of acrylic polymers. In some embodiments, the first monomer is used in an amount of at least 80%, 85%, 90%, 92%, 95%, 97%, 98% or 99% by weight based on the total weight of the monomer, and the second monomer is used in an amount of at most 20%, 15%, 10%, 8%, 5%, 3%, 2% or 1% by weight based on the total weight of the monomer. These percentages also reflect the percentages of various monomeric units in the acrylic polymer. When present, the multifunctional crosslinking monomer may be used in an amount of 0.002 to 2 parts per hundred parts of monofunctional monomer, such as about 0.01 to about 0.5 parts or about 0.05 to 0.15 parts per hundred parts of monofunctional monomer.

[0063] The vehicle can include any of these monomers, a polymer made from any of these monomers, or a combination thereof.

[0064] When the vehicle includes monomers, polymerization of these monomers can be achieved by various conventional free radical polymerization methods (e.g., solvent polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization), which can be chemically, thermally, and / or radiation-initiated. Polymerization can be initiated by actinic radiation (e.g., visible light or ultraviolet light), electron beam radiation, and combinations thereof.

[0065] The vehicle may also include a free radical initiator, such as a thermal initiator and a photoinitiator. Certain photoinitiators may be consumed when reacting with light during use, and may not be present in the foam composition of the present disclosure. In some embodiments, the foam composition also includes a photoinitiator or a fragment thereof. Any suitable photoinitiator may be used in a foam composition, which includes at least one acrylic monomer, for example, the first acrylic monomer and the second acrylic monomer as described in any embodiment of the embodiment above. Suitable photoinitiators include type I or type II photoinitiators. Suitable photoinitiators may include acetophenone, benzilketal, alkylaminoacetophenone, benzoylphosphine oxide, benzoin ether, benzophenone and benzoyl formate. In some embodiments, the free radical photoinitiator is a type I (cleavage type) photoinitiator. Cleavage type photoinitiators include acetophenone, α-aminoalkylphenone, benzoin ether, benzoyl oxime, acyl (e.g., benzoyl) phosphine oxide, acyl (e.g., benzoyl) phosphinate and mixtures thereof.

[0066] Examples of usable benzoin ethers include benzoin methyl ether and benzoin butyl ether. Examples of suitable acetophenone compounds include 4-diethylaminoacetophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,2-dimethoxy-1,2-diphenylethan-1-one. Examples of suitable acylphosphine oxides, acylphosphinates and acylphosphonate compounds 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, dimethyl pivaloylphosphonate 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 also be used together in any combination. The photoinitiator may be selected, for example, based on the desired curing wavelength and compatibility with the composition.

[0067] Examples of suitable thermal initiators include peroxides (e.g., benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, cyclohexane peroxide, and methyl ethyl ketone peroxide), hydroperoxides (e.g., butyl hydroperoxide and isopropylbenzene hydroperoxide), dicyclohexyl peroxydicarbonate, tert-butyl perbenzoate, and azo compounds (such as 2,2-azo-bis(isobutyronitrile) (AIBN)), and combinations thereof. Examples of commercially available thermal initiators include those available under the trade designation "VAZO" from The Chemours Company (Wilmington, Delaware) (such as VAZO 64 (2,2'-azobis(isobutyronitrile)), "VAZO 52", "VAZO 65", and "VAZO 68"); and those available under the trade designation "CELOGEN" from CelChem LLC, Naples, Florida. Peroxides are available from a variety of sources.

[0068] The initiator is used in an amount effective to promote polymerization of the monomers present in the vehicle, and the amount varies depending on, for example, the type of initiator, the molecular weight of the initiator, the intended application of the resulting adhesive composition, and polymerization process factors such as temperature. The photoinitiator can be used in any amount effective to promote polymerization of the monomers (e.g., 0.1 to about 5 parts, 0.2 to about 2 parts, or about 0.1 to about 1 part per one hundred parts of monofunctional monomers used to make the acrylic polymer).

[0069] In some embodiments, the vehicle includes a photoinitiator, which can be considered a photocrosslinker. Examples of suitable photocrosslinkers include ethylenically unsaturated compounds capable of abstracting hydrogen in an excited state (e.g., acrylated benzophenones, such as described in U.S. Pat. No. 4,737,559 (Kellen et al.)); Company, Exton, PA); monomers described in U.S. Pat. No. 5,073,611 (Rehmer et al.), including p-N-(methacryloyl-4-oxopentamethylene)-carbamoyloxybenzophenone, N-(benzoyl-p-phenylene)-N'-(methacryloyloxymethylene)-carbodiimide and p-acryloyloxybenzophenone) and p-acryloyloxyethoxybenzophenone; monofunctional benzophenones (e.g., benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-di ... benzophenone); polyfunctional benzophenones (e.g., carboxymethoxybenzophenone and the diester of polytetramethylene glycol 250); anthraquinone photocrosslinkers (e.g., anthraquinone, 2-methylanthraquinone, 2-tert-butylanthraquinone, 2-ethylanthraquinone, 2-phenylanthraquinone, 1,4-dimethylanthraquinone, 2,3-dimethylanthraquinone, 1,2-dimethylanthraquinone, l-methoxy-2-methylanthraquinone, 2-acetylanthraquinone and 2,6-di-tert-butylanthraquinone); thioxanthone photocrosslinkers (including thioxanthone, 2-isopropylthioxanthone, 2-Chlorothioxanthone, 2-dodecylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-benzenesulfonylthioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinylethyl)-thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxymethyl)thioxanthone, methoxybenzyl)-thioxanthone, 2-morpholinylmethylthioxanthone, 2-methyl-6-morpholinylmethylthioxanthone, N-propenylthioxanthone-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-triazine (e.g., 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, as described in U.S. Pat. No. 4,330,590 (Vesley); and 2,4-bis(trichloromethyl)-6-naphthyl-s-triazine and 2,4-bis(trichloromethyl)-6-(4-methoxy)naphthyl-s-triazine, as described in U.S. Pat. No. 4,329,384 (Vesley). The photocrosslinker may be present in the acrylic polymer in any useful amount. For example, an amount of 0.001 to 10 parts, 0.001 to 5 parts, 0.001 to 2 parts, 0.001 to 1 part, 0.001 to 0.5 parts, or 0.001 to 0.1 parts per hundred parts of monofunctional monomer can be used for the vehicle, which includes at least one acrylic monomer (e.g., the first acrylic monomer and the second acrylic monomer as described above in any of their embodiments). ;

[0070] The polymerizable vehicle composition may also include a chain transfer agent. The chain transfer agent may be selected to be soluble in the monomer mixture to be polymerized. Examples of suitable chain transfer agents include triethylsilane and mercaptans.

[0071] In some embodiments of the foam composition of the present disclosure and / or the foam composition manufactured by the method of the present disclosure, the vehicle includes or is derived from a composition comprising at least one acrylic monomer (e.g., a first acrylic monomer and a second acrylic monomer as described above in any embodiment of any of them) and a polymer manufactured by partial polymerization of the at least one acrylic monomer. The vehicle can be a solution of a polymer in at least one monomer, and can be, for example, about 3% to 15% polymerized. In some embodiments, the vehicle includes at least 75%, 80%, 85%, 90%, or 95% by weight of monomers based on the total weight of the vehicle. In some embodiments, the vehicle is exposed to ultraviolet radiation to provide a solution of a polymer in at least one acrylic monomer. A solution of a polymer in at least one acrylic monomer can also be manufactured by partial free radical polymerization using a thermal initiator or other free radical source.

[0072] Useful solventless polymerization methods are disclosed in U.S. Pat. No. 4,379,201 (Heilmann et al.). Initially, a mixture of the first and second monomers can be polymerized with a portion of the photoinitiator by exposing the mixture to UV radiation in an inert environment for a time sufficient to form a coatable base syrup, and then adding a crosslinker and the remainder of the photoinitiator. The crosslinking can be, for example, any of the above-described multifunctional crosslinking monomers in any of the amounts described above. This final syrup containing the crosslinker (e.g., which can have a Brookfield viscosity of about 500 centipoise (cps) to about 10,000 cps at 23° C., about 100 cps to about 6000 cps at 23° C., or about 5,000 cps to about 7,500 cps at 23° C., as measured with a No. 4 LTV spindle at 60 rpm) can then be coated onto a substrate. After the slurry is coated on the substrate, further polymerization and crosslinking can be carried out in an inert environment (such as nitrogen, carbon dioxide, helium and argon, excluding oxygen). A sufficiently inert atmosphere can be achieved by covering a layer of the photosensitive slurry with a polymer film (such as a silicone-treated PET film that is transparent to UV radiation or electron beam irradiation).

[0073] Any suitable light source can be used, including fluorescent UV bulbs, mercury lamps (e.g., low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps), xenon lamps, metal halide lamps, electrodeless lamps, incandescent lamps, LEDs, and lasers. For broadband light sources (e.g., fluorescent UV bulbs, mercury lamps, or incandescent lamps), filters can be used to narrow the wavelength range to within or outside the wavelength absorbed by the ultraviolet light absorber and / or to change the intensity of the light source.

[0074] The vehicle and / or foam composition may also include other ingredients such as curing agents, curing accelerators, catalysts, tackifiers, plasticizers, dyes, flame retardants, adhesion promoters (e.g., coupling agents such as silane coupling agents), pigments, impact modifiers, flow control agents, blowing agents, fillers (e.g., talc, zinc oxide and fused silica), glass and polymer microspheres and microparticles, conductive particles, thermally conductive particles, fibers, antistatic agents, antioxidants such as hindered phenols, amines and sulfur and phosphorus hydroperoxide decomposers, UV absorbers, stabilizers (e.g., hindered amine light stabilizers and heat stabilizers); and viscosity modifiers such as fumed silica.

[0075] The foam compositions of the present disclosure and / or the foam compositions made by the methods of the present disclosure may include hollow microspheres (e.g., hollow ceramic (e.g., glass) microspheres or hollow polymer microspheres, such as elastomeric particles available under the trade name "EXPANCEL" from Akzo Nobel, Amsterdam, The Netherlands. Examples of hollow ceramic microspheres include alumina / silica microspheres having a particle size ranging from 5 microns to 300 microns and a specific gravity of 0.7 ("FILLITE", Pluress-Stauffer International), aluminum silicate microspheres having a specific gravity of about 0.45 to about 0.7 ("Z-LIGHT"), calcium carbonate-coated polyvinylidene copolymer microspheres having a specific gravity of 0.13 ("DUALITE 6001AE", Pierce & Stevens Corp.), and 3M Company, Saint Paul, Minnesota. Paul, Minnesota) as "3M GLASS BUBBLES" of 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". Foams containing hollow microspheres are referred to as composite foams. The foaming adhesive may also include a hydrocarbon elastomer as described in U.S. Pat. No. 5,024,880 (Vesley et al.).

[0076] In some embodiments, the vehicle comprising the adhesive composition includes a tackifier, which can be used to increase the stickiness of the PSA surface. In some embodiments, the foam composition does not contain a tackifier. Useful tackifiers have a number average molecular weight of up to 10,000 g / mol, a softening point of at least 70° C. (as determined using a ring and ball instrument), and a glass transition temperature of at least -30° C. (as determined by differential scanning calorimetry). Useful tackifiers are generally amorphous. In some embodiments, the tackifier is miscible with the polymer of the PSA so that no macroscopic phase separation occurs in the PSA. In some embodiments, the PSA also does not have microscopic phase separation. In some embodiments, the tackifier comprises at least one of rosin, rosin esters, 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., based on styrene, α-methylstyrene, methylindene, indene, coumarone, or combinations thereof), or mixed aliphatic-aromatic hydrocarbon resins. Any of these tackifying resins may be hydrogenated (e.g., partially or fully). Examples of suitable tackifiers include those available under the trade designation "FLORAL" (including FORAL 85E) (glycerol ester of highly hydrogenated refined gum rosin) from Eastman, Middelburg, NL, those available under the trade designation "FORAL 3085" (glycerol ester of highly hydrogenated refined wood rosin) from Pinova, Brunswick, GA; "ESCOREZ", including "ESCOREZ 2520" and "ESCOREZ 5615 (aliphatic / aromatic hydrocarbon resins), commercially available from ExxonMobil Corp., Houston, TX; "ARKON" such as "ARKON P125", a fully hydrogenated hydrocarbon resin, available from Arakawa Chemical Co., Chicago, IL. Inc., Chicago, Illinois), and "REGALITE" such as "REGALITE 7100" (a partially hydrogenated hydrocarbon resin) is commercially available from Eastman, Kingsport, Tennessee.

[0077] In some embodiments, the vehicle comprises at least about 1 wt % and up to about 50 wt % of a tackifier based on the total weight of the vehicle. In some embodiments, the tackifier is present in a range of 1-25 wt %, 2-20 wt %, 2-15 wt %, 1-10 wt % or 3-10 wt % based on the total weight of the vehicle.

[0078] Plasticizers may be added, for example, to reduce the vitrification of the adhesive composition. Suitable plasticizers include various polyoxyolefins (e.g., polyethylene oxide or propylene oxide), adipates, formates, phosphates, benzoates, phthalates, polyisobutylene, polyolefins and sulfonamides, naphthenic oils, plasticizing aids (such as those described as plasticizers in "Dictionary of Rubber", KF Heinisch, page 359, John Wiley Sons, New York (New York) (1974)), oils, elastomeric oligomers and waxes. The amount of the plasticizer used (if used) will depend on the nature of the plasticizer and the compatibility of the plasticizer with the vehicle.

[0079] In some embodiments, the foam compositions of the present disclosure and / or foam compositions made by the methods of the present disclosure are substantially free of solvents. Commonly used organic solvents include aliphatic and alicyclic hydrocarbons (e.g., hexane, heptane and cyclohexane), hydrocarbon solvents (e.g., benzene, toluene, xylene and d-limonene); non-cyclic and cyclic ketones (e.g., acetone, methyl ethyl ketone and methyl isobutyl ketone, pentanone, hexanone, cyclopentanone and cyclohexanone); ethers (e.g., ethyl 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., methanol, ethanol, or propanols such as (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%, or 0.01% by weight of any of these solvents, or may be free of any of these solvents. These percentages are based on the total weight of the foam composition.

[0080] In some embodiments, the vehicle includes a silane coupling agent. Examples of useful silane coupling agents include organosilanes such as alkylchlorosilanes, alkoxysilanes (e.g., methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, phenyltriethoxysilane, polytriethoxysilane, vinyltrimethoxysilane, Vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, vinyltri(tert-butoxy)silane, vinyltri(isobutoxy)silane, vinyltri(isopropenyloxy)silane, and vinyltri(2-methoxyethoxy)silane); N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate; N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethylcarbamate; silane functional (Meth)acrylates (e.g., 3-(methacryloxy)propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloxy)propyltriethoxysilane, 3-(methacryloxy)propylmethyldimethoxysilane, 3-(acryloxypropyl)methyldimethoxysilane, 3-(methacryloxy)propyldimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-(methacryloxy)propyldimethylethoxysilane, and 3-(methacryloxy)acryltrimethoxysilane) ; Epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethoxydimethoxysilane, 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 relative to the total weight of the vehicle.

[0081] In some embodiments, the foam composition of the present disclosure and / or the foam composition made by the method 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 blowing agents or organic blowing agents. Useful chemical foaming mechanisms include in situ generation of gas by chemical reaction; decomposition of components of the composition, e.g., components that release gas upon thermal decomposition; evaporation of components of the composition, e.g., liquid gas; volatilization of gas in the composition by reducing the pressure on the composition or heating the composition; and combinations thereof.

[0082] Examples of chemical blowing agents include water, azo-based molecules, carbonate-based molecules, and hydrazide-based molecules (including, for example, 4,4'-oxybis(benzenesulfonyl)hydrazine, 4,4'-oxybenzenesulfonyl semicarbazide, azoformamide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, azobisisobutyronitrile, benzenesulfonylhydrazide, trihydrazinotriazine, metal salts of azodicarboxylic acids, oxalic acid hydrazide, hydrazine nitrogen carboxylate, diphenyl ether-4,4'-disulfonylhydrazide, tetrazole compounds, sodium bicarbonate, ammonium bicarbonate, carbonate (or ester) compounds, and preparations of polycarbonates, mixtures of citric acid and sodium bicarbonate, N,N'-dimethyl-N,N'-dinitroso-terephthalamide, N,N'-dinitrosopentamethylenetetramine, and combinations thereof. Water is a blowing agent that can be used to make polyurethane foams. Water reacts with isocyanates to ultimately form carbon dioxide, which causes polyurethane to foam.

[0083] Suitable inorganic physical blowing agents include, for example, nitrogen, argon, oxygen, water, air, helium, sulfur hexafluoride, and combinations thereof.

[0084] Available organic physical blowing agents include carbon dioxide, aliphatic hydrocarbons, aliphatic alcohols, completely and partially halogenated aliphatic hydrocarbons, including for example methylene chloride, and combinations thereof. Examples of suitable aliphatic hydrocarbon blowing agents include members of the hydrocarbons of the alkane series, including for example methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and blends thereof. Available aliphatic alcohols include for example methanol, ethanol, n-propyl alcohol, isopropyl alcohol and combinations thereof. Suitable completely or partially halogenated aliphatic hydrocarbons include for example fluorocarbons, chlorocarbons and chlorofluorocarbons and combinations thereof.

[0085] 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, and difluorocyclopentane. Butane, 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 non-halogenated. In some embodiments, the blowing agent is non-fluorinated.

[0086] The blowing agent can be used as a single component, in mixtures and combinations thereof, and in mixtures with other co-blowing agents.The blowing agent is added to the composition in an amount sufficient to achieve the desired foam density.

[0087] In some embodiments, the foam composition of the present disclosure and / or the foam composition manufactured by the method of the present disclosure further comprises a nucleating agent. The nucleating agent can be any conventional nucleating agent. The amount of the nucleating agent to be 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 the form of small particles include clay, talc, silicon dioxide and diatomaceous earth.

[0088] Organic nucleating agent can decompose or react at a given temperature. An example of organic nucleating agent is a combination of an alkali metal salt of a polycarboxylic acid with a carbonate or bicarbonate. Examples of available alkali metal salts of polycarboxylic acids include monosodium salts (i.e., sodium hydrogen tartrate) of 2,3-dihydroxy-butenedioic acid, monopotassium salts (i.e., potassium hydrogen succinate) of butenedioic acid, trisodium salts (i.e., sodium citrate) and tripotassium salts (i.e., potassium citrate) of 2-hydroxy-1,2,3-propanetricarboxylic acid, disodium salts (i.e., sodium oxalate) of oxalic acid 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. An expected combination is a monoalkali metal salt (such as, monosodium citrate or monosodium tartrate) of a polycarboxylic acid with a carbonate or bicarbonate. It is expected that a mixture of different nucleating agents can be added to a vehicle. Other useful nucleating agents include a stoichiometric mixture of citric acid and sodium bicarbonate.

[0089] In some embodiments, the foam half-life of the foam composition of the present disclosure at 22°C is at least 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes or 60 minutes. In the present application, the foam half-life is determined by the following method: about 30 grams of a 1% by weight solution of a silicone MQ resin, alone or in combination with a surfactant, is placed in a 4-ounce glass jar containing a vehicle, and nitrogen is bubbled through the mixture for five minutes at 22°C using the apparatus described in the slurry bubble test in the examples, while stirring the mixture with a magnetic stir bar set at a low setting. The bubbling is stopped and the magnetic stir bar is turned off. The foam height is measured with a ruler. The time required for half of the liquid to be discharged from the foam (i.e., half of the initial volume of liquid) is measured to provide the foam half-life.

[0090] As shown in the comparison of Examples 1 to 13 with Comparative Examples CE1 to CE12 below in the Examples, silicone MQ resins reported as defoamers or antifoaming agents are surprisingly good foam stabilizers in a vehicle of acrylic monomers. In fact, silicone MQ resins are shown to be better foam stabilizers than a variety of surfactants, which are expected to be more suitable for stabilizing foam. As shown in the comparison of Examples 11 and 12 with Comparative Examples 13 and 14 below in the Examples, silicone MQ resins reported as defoamers or antifoaming agents do not adversely affect the foaming ability of certain silicone and hydrocarbon surfactants in a vehicle of acrylic monomers. In fact, silicone MQ resins are shown to enhance the foaming ability of the surfactant in Example 12.

[0091] The present disclosure provides a method for manufacturing a foam composition of the present disclosure as described above in any embodiment thereof. The method includes introducing a foaming agent into a composition comprising a vehicle and a silicone MQ resin to form a void in the composition. The foaming agent can be any of the above-mentioned chemical or physical foaming agents. The composition can be foamed according to a variety of foaming methods (including, for example, the foaming methods described in U.S. Patents No. 5,024,880 (Vesley et al.), No. 4,895,745 (Vesley et al.) and No. 4,748,061 (Vesley et al.)).

[0092] The composition can be foamed by forming gas voids in the composition using a variety of mechanisms (including mechanical mechanisms, chemical mechanisms and combinations thereof). Available mechanical foaming mechanisms include stirring (e.g., shaking, stirring and oscillating the composition), injecting gas into the composition (e.g., inserting a nozzle below the surface of the composition and blowing gas into the composition, and combinations thereof). In some embodiments, introducing a foaming agent includes stirring the composition or injecting gas into the composition. In some embodiments, the foaming agent includes at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon or nitrous oxide.

[0093] The foam compositions of the present disclosure and / or the foam compositions made by the methods of the present disclosure are suitable for a variety of applications. Representative examples of foam applications include adhesives, flotation, applications in the automotive industry (including automotive body moldings), applications related to automotive glazing (including gaskets and sealants), applications in the construction industry (including structural components (e.g., sizing wood, formed trim, columns, beams, and formed structural members)), lightweight ceramics (including precast and cast-in-place building materials, including cementitious materials and gypsum materials such as blocks, boards, panels, roof panels, and flooring), landfill covers, odor barriers, dust covers, firefighting and fire protection foams, liquid containment booms (e.g., oil spill containment booms), and fillers for voids such as oil wells and tunnels and voids present in soil. Other foam applications include packaging, commercial cleaning products (including cleaners for vertical cleaning applications), inks, deinking compositions, surface coatings (including foaming coatings for, for example, paper and textile treatments).

[0094] The foam compositions can also be formulated for use in medical applications, including bandages and wound dressings, and household and industrial applications, including cups, plates, earplugs, cushions, pillows, insulation, dampers (e.g., for dampening sound, absorbing vibrations (e.g., cushioning hood vibrations)), and combinations thereof, and baffles.

[0095] In another embodiment, the foam composition is formulated to be useful as a gasket or seal to seal an area from, for example, dust, moisture, organic vapors, and combinations thereof. Examples of sealing applications include sealing gaps between components in computer printers, sealing electronic devices, and sealing sunroof assemblies.

[0096] The foam composition can be formulated to provide flexible and conformable foams suitable for filling gaps and bonding irregular surfaces. The foam can also be formulated to provide an adhesive layer that seals, cushions vibrations, dampens vibrations, resists shock, withstands a wide temperature range, or provides good insulating qualities, or a combination of these properties.

[0097] The foam composition can be in the form of a tape such as a pressure-sensitive adhesive tape. Available foam tape constructions include a foam composition disposed on a substrate (e.g., a backing or a release liner), and are optionally wound in the form of a roll. In some embodiments, the foam tape construction includes an adhesive composition disposed on the surface of the foam tape, which forms a tape with an adhesive layer on one side of the foam tape, i.e., a single-layer coated adhesive foam tape. In another embodiment, the foam composition can be in the form of a tape with an adhesive layer on both major surfaces of the foam tape, which is referred to as a double-layer coated foam tape.

[0098] The present disclosure provides a method for making an adhesive tape, the method comprising applying a foam composition to a substrate. The foam composition may be applied to the substrate after the foam composition is foamed using any of the above methods, i.e., after a void is formed therein. The foam composition may be applied to the substrate using a variety of methods (e.g., dipping, spraying, brushing, roller coating, rod coating). In some embodiments, the composition may be applied to the liner using a notched rod having a gap setting for providing a desired thickness above the liner, and another liner may be added to maintain a gap of the desired thickness. Although any of the foam compositions described above in any of their embodiments may be applied to a substrate, in some embodiments, the vehicle comprises a monomer and an optional polymer, and the method further comprises polymerizing the monomer. In some embodiments, the method further comprises crosslinking the foam composition. When a UV light source such as any of the light sources described above is used for polymerization or crosslinking, any useful amount of UV irradiation may be employed, such as approximately 1,000 mJ / cm 2 Up to about 10,000mJ / cm 2 、1,000mJ / cm 2 Up to about 5,000mJ / cm 2 or about 1,000mJ / cm 2 Up to about 3,000mJ / cm 2 .

[0099] Adhesive foams have a variety of useful applications, including, for example, bonding two substrates together; mounting applications using articles including hooks, hangers and brackets; joining applications including bonding two or more containers (e.g., boxes) together for later separation; bonding articles to surfaces (e.g., walls, floors, ceilings and counters) and replacing mechanical fasteners, fillers or liquid glues. When bonding rough or irregular surfaces, the properties and formulation of the foam tape can be selected to provide a foam tape that evenly distributes stress over the bonded area. Other adhesive foam applications include, for example, as a structural adhesive and a foam-in-place adhesive.

[0100] In other embodiments, the foam composition includes other components, such as scrims, films, tissues, and combinations thereof, dispersed in the foam or disposed in a layered configuration with the foam composition, for example, in alternating layers, interpenetrating layers, and combinations thereof. Other useful foam configurations include multilayer foam configurations including foam layers, wherein the layers differ in at least one property, including, for example, density and composition.

[0101] The foam composition may also be subjected to post-processing including, for example, die cutting, cross-linking, and sterilization.

[0102] Some embodiments of the present disclosure

[0103] In a first embodiment, the present disclosure provides a foam composition comprising: a vehicle having voids therein, wherein the vehicle comprises at least one of a silicone-free organic polymer or an organic monomer and a silicone MQ resin, wherein the foam composition comprises no more than 50 wt % water. In a second embodiment, the present disclosure provides a foam composition according to the first embodiment, wherein the foam composition comprises no more than 40 wt %, 30 wt %, 20 wt %, 10 wt %, 5 wt %, 4 wt %, 3 wt %, 2 wt % or 1 wt % water. In a third embodiment, the present disclosure provides a foam composition according to the first embodiment or the 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 a foam composition according to any one of the first to third embodiments, wherein the silicone MQ resin has an M:Q ratio of no more than 2.5:1 or 2:1. In a fifth embodiment, the present disclosure provides a foam composition according to any one of the first to fourth embodiments, wherein the foam composition is provided by one or more of the formula (R)3-Si-R 1 A compound represented by and one or more compounds represented by formula (R 1)4Si, wherein each R is independently hydrogen, alkyl, aryl, alkylene group subjected to at least one of insertion or end-capping by arylene group or heterocyclylene group, wherein the alkyl and alkylene group subjected to at least one of insertion or end-capping by arylene group or heterocyclylene group are unsubstituted or substituted by halogen and are optionally inserted by at least one chain -O-, -NR'-, -S-, -Si- or a combination thereof, and wherein the aryl, arylene and heterocyclylene groups are unsubstituted or substituted by at least one alkyl, alkoxy, halogen or a combination thereof, and wherein each R 1 R may not be hydrogen. R may not contain an alkyleneoxy group, such as -(OR 2 ) n -OR 3 Group, where n, R 2 and R 3 As defined below in any of their 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 comprises 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 hydroxyl content of the silicone MQ resin is in the range of 185 milliequivalents / kg to 1840 milliequivalents / kg. In an eighth embodiment, the present disclosure provides a foam composition according to any one of the first to seventh embodiments, wherein the silicone MQ resin is present in the foam composition in an amount of 0.1 wt % to 10 wt %, 0.1 wt % to 5 wt % or 0.5 wt % to 5 wt % 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, the foam composition further comprising a polyoxyalkylene-modified polydimethylsiloxane. In a tenth embodiment, the present disclosure provides a foam composition according to the ninth embodiment, wherein the polyoxyalkylene-modified polydimethylsiloxane comprises a repeating divalent unit represented by formula II:

[0104] and by the formula -Q-(OR 2 ) n -OR 3 At least one of the terminal units represented by or a divalent unit represented by formula III:

[0105] wherein each Q is independently an alkylene group, an arylene group, or an alkylene group subjected to at least one of insertion or end-capping by an aryl group, one of which is optionally subjected to at least one of insertion or end-capping by at least one of the following groups: at least one ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, or thiourea, each OR 2 are 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 is 3 is hydrogen, alkyl, acyl, aryl or arylalkylene, wherein aryl and arylalkylene are unsubstituted or substituted by at least one alkyl, alkoxy or combination thereof. In the eleventh embodiment, the present disclosure provides a foam composition according to the ninth embodiment or the tenth embodiment, wherein the number average molecular weight of the polyoxyalkylene-modified polydimethylsiloxane is not greater than 50,000 g / mol, 40,000 g / mol, 30,000 g / mol, 20,000 g / mol or 10,000 g / mol. In the twelfth embodiment, the present disclosure provides a foam composition according to any one of the ninth to eleventh embodiments, wherein the polyoxyalkylene-modified polydimethylsiloxane comprises ethyleneoxy groups, propyleneoxy groups or combinations thereof. In the thirteenth embodiment, the present disclosure provides a foam composition according to any one of the first to twelfth embodiments, the foam composition further comprising an alkoxylated alcohol. In the fourteenth embodiment, the present disclosure provides a foam composition according to the thirteenth embodiment, wherein the alkoxylated alcohol is an alkoxylated hydrocarbon alcohol. In a fifteenth embodiment, the present disclosure provides a foam composition according to the thirteenth embodiment or the fourteenth embodiment, wherein the alkoxylated alcohol is an ethoxylated hydrocarbon alcohol. In a sixteenth embodiment, the present disclosure provides a foam composition according to any one of the ninth embodiment to the fifteenth embodiment, wherein the silicone MQ resin and at least one of the polyoxyalkylene-modified polydimethylsiloxane or the alkoxylated alcohol are present in the foam composition in a combined amount of 0.1 wt % to 10 wt %, 0.1 wt % to 5 wt %, or 0.5 wt % to 5 wt %, based on the total weight of the foam composition.

[0106] In the seventeenth embodiment, the present disclosure provides a foam composition according to any one of the first to sixteenth embodiments, wherein the vehicle comprises at least one of a thermoplastic polymer, a thermosetting polymer, or an elastomer. In the eighteenth embodiment, the present disclosure provides a foam composition according to any one of the first to seventeenth embodiments, wherein the vehicle comprises at least one of a polyester, a polyurethane, an amino resin, an alkyd resin, a phenolic resin, an epoxy resin, an isocyanate resin, an isocyanurate resin, or an acrylic polymer. In the nineteenth embodiment, the present disclosure provides a foam composition according to any one of the first to eighteenth embodiments, wherein the vehicle comprises a cross-linked polymer. In the twentieth embodiment, the present disclosure provides a foam composition according to any one of the first to nineteenth embodiments, wherein the vehicle comprises at least one of an acrylate or an acrylic polymer. In the twenty-first embodiment, the present disclosure provides a foam composition according to any one of the first to twentieth embodiments, wherein the vehicle comprises at least one of a mixture of at least two or at least three structural isomers of isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, butyl acrylate, acrylic acid, or a secondary alkyl ester of (meth) acrylic acid of formula (VI):

[0107]

[0108] Where R 7 and R 8 Each independently is C1 to C 30 Saturated straight chain alkyl group; R 7 and R 8 The sum of the number of carbon atoms is 7 to 31, and R 5A polymer of a unit containing hydrogen or a methyl group, or any of these groups. In the twenty-second embodiment, the present disclosure provides a foam composition according to any one of the first embodiment to the twenty-first embodiment, wherein the vehicle includes acrylic acid and at least one of isooctyl acrylate or 2-ethylhexyl acrylate. In the twenty-third embodiment, the present disclosure provides a foam composition according to any one of the first embodiment to the twenty-second embodiment, wherein the vehicle includes a polyolefin. In the twenty-fourth embodiment, the present disclosure provides a foam composition according to any one of the first embodiment to the twenty-third embodiment, wherein the vehicle includes at least one of a novolac resin, a resol phenolic resin, or a polyurea resin. In the twenty-fifth embodiment, the present disclosure provides a foam composition according to any one of the first embodiment to the twenty-fourth embodiment, wherein the vehicle includes at least one of an isocyanate, a polyurethane, or a polyurea. In the twenty-sixth embodiment, the present disclosure provides a foam composition according to any one of the first embodiment to the twenty-fifth embodiment, wherein the vehicle includes at least one of an alcohol, an aldehyde, a ketone, an ester, an ether, an amine, an amide, or a hydrocarbon.

[0109] In the twenty-seventh embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-sixth embodiments, wherein the vehicle has voids therein. In the twenty-eighth embodiment, the present disclosure provides a foam composition according to the twenty-seventh embodiment, wherein the voids contain at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide. In the twenty-ninth embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-eighth embodiments, the foam composition further comprising a foaming agent. In the thirtieth embodiment, the present disclosure provides a foam composition according to the twenty-ninth embodiment, wherein the foaming agent includes at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide. In the thirty-first embodiment, the present disclosure provides a foam composition according to any one of the first to thirtieth embodiments, the foam half-life of the foam composition at 22° C. being at least 10 minutes. In the thirty-second embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-first embodiments, the foam composition further comprising at least one of fumed silica, hollow ceramic microspheres, or hollow polymer microspheres. In a thirty-third embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-second embodiments, wherein the foam composition is free of a fluorinated surfactant.

[0110] In a thirty-fourth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-third embodiments, wherein the vehicle comprises an adhesive composition. In a thirty-fifth embodiment, the present disclosure provides a foam composition according to the thirty-fourth embodiment, wherein the vehicle comprises a pressure-sensitive adhesive composition. In a thirty-sixth embodiment, the present disclosure provides a foam composition according to the thirty-fourth embodiment, wherein the vehicle comprises a hot melt adhesive composition. In a thirty-seventh embodiment, the present disclosure provides an adhesive tape comprising the foam composition according to any one of the thirty-fourth to thirty-sixth embodiments. In a thirty-eighth embodiment, the present disclosure provides an article comprising the foam composition according to any one of the first to thirty-sixth embodiments.

[0111] In the thirty-ninth embodiment, the present disclosure provides a method for manufacturing the adhesive tape according to the thirty-seventh embodiment, the method comprising applying the foam composition to a substrate. In the fortieth embodiment, the present disclosure provides a method according to the thirty-ninth embodiment, wherein the vehicle comprises an organic monomer and an optional silicone-free organic polymer, and the method further comprises polymerizing the organic monomer. In the forty-first embodiment, the present disclosure provides a method according to the thirty-ninth embodiment or the fortieth embodiment, the method further comprises crosslinking the foam composition. In the forty-second embodiment, the present disclosure provides a method for manufacturing a foam composition according to any one of the first to thirty-sixth embodiments, the method comprising introducing a foaming agent into a composition comprising a vehicle and a silicone MQ resin to form a void in the composition. In the forty-third embodiment, the present disclosure provides a method according to the forty-second embodiment, wherein the introduction of a foaming agent comprises stirring the composition or injecting at least one of a gas into the composition. In the forty-fourth embodiment, the present disclosure provides a method according to the forty-third embodiment, wherein the foaming agent comprises at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon or nitrous oxide.

[0112] The following specific, non-limiting examples will serve to illustrate the present disclosure.

[0113] Example

[0114] Unless otherwise indicated, all parts, percentages, ratios, etc. in the examples and the remainder of this specification are by weight. The following abbreviations are used in this section: g = gram, cm = centimeter, Ga = gage, LPM = liter / minute, mM = millimole, mm = milliliter, mL = milliliter, and NMR = nuclear magnetic resonance. The materials used in the examples and their sources are shown in Table 1 below.

[0115] Table 1. Materials list

[0116]

[0117]

[0118] M:Q ratio determination

[0119] Approximately 150 mg of sample was placed in a PTFE NMR tube and dissolved with 2 mL of CDCl3 containing 0.1 mM Cr(OAcAc)3. Si was collected on a 600 MHz JEOL NMR spectrometer with a 10 mm JEOL silicon-free probe. 29 NMR data. 29 The M region of the NMR spectrum (between 17 ppm and 5 ppm) was integrated to determine the M:Q ratio. 29 The Q region (between -90 ppm and -115 ppm) in the NMR spectrum was integrated. The M:Q ratio is the corresponding integration ratio. The data are shown in Table 4 below.

[0120] Determination of Molecular Weight of Polydimethylsiloxane Modified with Polyoxyalkylene

[0121] Approximately 150 mg of the resin was placed in a PTFE NMR tube and dissolved with 2 mL of CDCl3 containing 0.1 mM Cr(OAcAc)3. The Si spectra were collected on a 600 MHz JEOL NMR spectrometer with a 10 mm JEOL silicon-free probe. 29 NMR data to determine the number average molecular weight. The number average molecular weight of the silicone "EFKA SL3257" was determined to be 2135 g / mol.

[0122] Preparation of silicone MQ resin terminated with triethylsilyl groups (TES terminated MQ resin)

[0123] Silicone MQ resin "SQO-299" (10.0 g) was dissolved in heptane (10.0 g) and triethylsilane (2.0 g) was then added in a 100 mL round bottom flask. Thereafter, Pd / charcoal (0.1 g) (5.0 wt% Pd loading) was added to the above mixture at room temperature. The addition of Pd / charcoal resulted in a rapid release of hydrogen, indicating that the silanol was replaced by triethylsilyl groups. The reaction mixture was stirred for 24 hours. The reaction mixture was passed through a 0.5 micron glass filter to separate the Pd / charcoal from the reaction mixture. Finally, any unreacted triethylsilane was removed using vacuum to produce a triethylsilyl terminated MQ resin.

[0124] Examples 1 to 13 (EX 1 to EX 13) and Comparative Examples (CE 1 to CE 12)

[0125] In a tall glass sample vial, 0.20 g of silicone MQ resin (as shown in Table 4 below) was measured and added for EX 1 to EX10 and EX 13. For CE 1 to CE 12, 0.20 g of the surfactant shown in Table 4 below was added to the sample vial. For EX 11 and EX 12, 0.2 g of a 50:50 mixture of silicone MQ resin and surfactant shown in Table 4 below was added to the sample vial. Then 10.0 g of an acrylic monomer mixture (90 parts by weight 2-EHA: 10 parts by weight AA) was added to the sample vial. The sample vial was capped and then evaluated using the foam column screening test described below. The data is shown in Table 4 below.

[0126] Foam column screening test (manual agitation)

[0127] The prepared samples of the acrylic monomer mixtures containing Examples 1 to 13 and Comparative Examples CE 1 to CE 12 were thoroughly mixed by shaking the sample vials vigorously for 15 seconds and allowing the contents to settle. The sample vials were then placed on a horizontal surface. The foam height was visually measured using a ruler. Photos were taken and data was recorded immediately to record the height of the foaming column. The time required for half of the liquid to be drained from the foam (i.e., half of the initial volume of liquid) was measured and recorded as the foam half-life. The overall evaluation is further described in Table 2 below.

[0128] Table 2: Overall evaluation of foam height and foam persistence

[0129]

[0130] Examples 1A to 13A (EX 1A to EX 13A) and Comparative Examples (CE 1A to CE 12A) for Slurry Bubble Testing

[0131] A coatable viscosity slurry polymer was prepared by charging a one quart jar with 90 parts 2-EHA and 10 parts AA and "OMNIRAD 651" (0.04 parts per 100 parts monomer) and stirring until the photoinitiator was dissolved and a homogenous mixture was obtained. The mixture was degassed by introducing nitrogen into the mixture through a tube inserted into the opening in the jar lid and bubbling vigorously for at least 5 minutes. While stirring, the mixture was exposed to UV-A light until a pre-adhesive slurry was formed, which had a viscosity considered suitable for coating. After UV exposure, air was introduced into the bottle. The light source was an LED array with a peak emission wavelength of 365 nm.

[0132] In a 4 ounce glass jar equipped with a magnetic stirring bar, 30.0 g of slurry was weighed. Then, for EX 1A to EX10A and EX 13A, 0.30 g of silicone MQ resin (as shown in Table 4 below) was added to the glass jar. For CE 1A to CE12A, 0.30 g of surfactant shown in Table 4 below was added to the glass jar. For EX 11A and EX 12A, 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. The sample was then capped. The sample was stirred on a magnetic stirring plate for five minutes, and then the following slurry bubbling test was performed. The data is shown in Table 4 below.

[0133] Slurry Bubble Test

[0134] Set up a bubbling device. Connect the indoor nitrogen line to a Cole-Parmer 5LPM flowmeter. Connect the flowmeter to a pipe equipped with a long 18-gauge needle. Replace the prepared sample glass jar lid with a lid equipped with a glass adapter, which is a hollow tube attached through a hole in a standard jar lid. Insert the septum into the glass adapter along with the 16-gauge needle (for exhaust). Then insert the long 18-gauge needle into the septum. Then turn on the nitrogen and adjust the flow to 4LPM, and confirm that the exhaust needle is functional. Then stir the magnetic stir bar on a magnetic stir plate at the "low" setting. Then push the long needle to the bottom of the jar. Let the device bubble for five minutes. Then remove the needle and turn off the magnetic stir bar. Then re-cover the closed glass jar lid and let the glass jar be at surface level.

[0135] The foam height was visually measured using a ruler. Photos were taken and data was recorded immediately to document the foam column height and persistence. The time required for half of the liquid to drain from the foam (i.e., to provide half of the initial volume of liquid) was measured and recorded as the foam half-life. The overall evaluation is shown in Table 3 below.

[0136] Table 3: Foam height and foam persistence for slurry bubbling test

[0137]

[0138] na = not applicable because so little foam is produced

[0139] Various modifications and alterations of this disclosure may be made by those skilled in the art without departing from the scope and spirit of this disclosure, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein.

[0140] Table 4: Examples EX 1 to EX 13 and EX 1A to EX 13A and CE 1 to CE 12 and CE 1A to CE 12A Success and Results

[0141]

[0142]

[0143] a na = not applicable.

Claims

1. A foam composition, comprising: a vehicle having a void therein, wherein the vehicle comprises at least one of a non-silicone-containing organic polymer or an organic monomer; and Silicone MQ resin, The foam composition comprises no more than 50% by weight of water.

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

1.

3. The foam composition of claim 1 or 2, wherein the MQ resin comprises methyl groups and the hydroxyl content of the MQ resin is in the range of 185 milliequivalents / kg to 1840 milliequivalents / kg.

4. The foam composition of any one of claims 1 to 3, wherein the silicone MQ resin is present in the foam composition at a level of 0.1 wt% to 10 wt%, based on the total weight of the foam composition.

5. The foam composition according to any one of claims 1 to 4, further comprising a polyoxyalkylene-modified polydimethylsiloxane having a number average molecular weight of no greater than 50,000 g / mol, and wherein the oxyalkylene comprises ethyleneoxy groups, propyleneoxy groups, or combinations thereof.

6. The foam composition according to any one of claims 1 to 5, further comprising an ethoxylated alcohol.

7. A foam composition according to any one of claims 1 to 6, having a foam half-life of at least 10 minutes at 22°C.

8. The foam composition of any one of claims 1 to 7, further comprising at least one of fumed silica, hollow ceramic microspheres, or hollow polymer microspheres.

9. The foam composition of any one of claims 1 to 8, wherein the vehicle comprises a silicone-free organic polymer, and wherein the silicone-free organic polymer comprises at least one of a polyester, a polyurethane, a polyurea, an amino resin, an alkyd resin, a phenolic resin, an epoxy resin, an isocyanate resin, an isocyanurate resin, or an acrylic polymer.

10. The foam composition of any one of claims 1 to 9, wherein the vehicle comprises the silicone-free organic polymer, and wherein the silicone-free organic polymer is cross-linked.

11. The foam composition of any one of claims 1 to 10, wherein the vehicle comprises at least one of an acrylate or an acrylic polymer.

12. The foam composition according to any one of claims 1 to 11, wherein the vehicle comprises at least one of isooctyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, butyl acrylate, acrylic acid, a mixture of at least two or at least three structural isomers of a secondary alkyl (meth)acrylate of the formula: Or a polymer comprising units of at least one of 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 a secondary alkyl (meth)acrylate of the formula: Where R 7 and R 8 Each independently is C1 to C 30 Saturated straight chain alkyl group; R 7 and R 8 The sum of the number of carbon atoms in is 7 to 31; and R 5 is hydrogen or a methyl group.

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

14. An adhesive tape comprising the foam composition of claim 13.

15. A method for making a foam composition according to any one of claims 1 to 13, the method comprising introducing a blowing agent into a composition comprising the vehicle and the silicone MQ resin to form voids in the composition.

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