Foam compositions comprising surface modified nanoparticles and related articles and methods

Abstract

A foam composition includes a vehicle, surface modified nanoparticles disposed in the vehicle, and at least one of a silicone MQ resin or a polyoxyalkylene modified polydimethylsiloxane. The particle size of each nanoparticle is less than about 100 nanometers. The vehicle may have voids therein. 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 / 348,393, 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 surface-modified nanoparticles are capable of forming persistent foam in the presence of silicone MQ resins and or polyoxyalkylene-modified polydimethylsiloxanes. Compositions comprising surface-modified nanoparticles and silicone MQ resins are surprisingly capable of forming persistent foam, even though silicone MQ resins have been reported as defoamers. In some embodiments, compositions comprising surface-modified nanoparticles and polyoxyalkylene-modified polydimethylsiloxanes are surprisingly more capable of forming persistent foam than compositions comprising surface-modified nanoparticles and other surfactants. In some embodiments, compositions comprising surface-modified nanoparticles and polyoxyalkylene-modified polydimethylsiloxanes are surprisingly more capable of forming persistent foam than compositions comprising only surface-modified nanoparticles or polyoxyalkylene-modified polydimethylsiloxanes.

[0007] In one aspect, the present disclosure provides a foam composition comprising a vehicle, surface-modified nanoparticles having a particle size of no greater than 100 nanometers, and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane. In some embodiments, the foam composition has voids therein. The present disclosure provides a composition before, during, and after foaming thereof.

[0008] In another aspect, the present disclosure provides a foam composition comprising a vehicle, surface-modified nanoparticles having a particle size of no greater than 100 nanometers, and a silicone MQ resin. In some embodiments, the foam composition has voids therein. The present disclosure provides a composition before, during, and after foaming thereof.

[0009] In another aspect, the present disclosure provides an adhesive tape (eg, a pressure-sensitive adhesive tape) comprising the above-described foam composition.

[0010] 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.

[0011] In another aspect, the present disclosure provides a method for making the above-mentioned foam composition, the method comprising introducing a foaming agent into the composition to form voids in the composition, the composition comprising a vehicle, surface-modified nanoparticles having a particle size of no greater than 100 nanometers, and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane.

[0012] In another aspect, the present disclosure provides a method of making a tape, wherein the method comprises foaming a composition, and then applying the composition to a substrate, the composition comprising a vehicle, surface-modified nanoparticles having a particle size of no greater than 100 nanometers, and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane.

[0013] As used in this article:

[0014] 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 to include general categories of 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 ... " following 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).

[0015] The term "acrylic" refers to acrylic and methacrylic polymers, oligomers, and monomers.

[0016] 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.

[0017] 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).

[0018] "Alkylidene" is a polyvalent (eg, divalent or trivalent) form of an "alkyl" group as defined above.

[0019] "Arylalkylene" refers to an "alkylene" portion to which an aryl group is attached.

[0020] 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.

[0021] 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.

[0022] A "monomeric unit" of a polymer or oligomer is a segment of the polymer or oligomer derived from a single monomer.

[0023] 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 a suitable solvent. The term "crosslinking" includes partial crosslinking. Thermosetting polymers are crosslinked.

[0024] The term "surface-modified nanoparticle" refers to a particle that comprises surface groups attached to the surface of the particle. The surface groups modify the properties of the particle.

[0025] 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.

[0026] The terms "particle diameter" and "particle size" refer to the largest cross-sectional dimension of a particle. If the particles are present in the form of aggregates, the terms "particle diameter" and "particle size" refer to the largest cross-sectional dimension of the aggregates.

[0027] The term "ceramic" refers to glasses, crystalline ceramics, glass-ceramics, and combinations thereof.

[0028] 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

[0029] The foam composition of the present disclosure and / or the foam composition that can be used for the method of the present disclosure include surface-modified nanoparticles having a particle size of less than 100 nanometers placed in a vehicle. In some embodiments, the foam composition includes voids in the vehicle, which may be present at the surface of the composition, dispersed throughout the composition, or a combination of the two. 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.

[0030] The surface-modified nanoparticles useful in the foam compositions and methods disclosed herein are individual, unassociated (i.e., non-aggregated) nanoparticles that are dispersed throughout the vehicle and do not irreversibly associate with one another. The terms "associated" or "bound" include, for example, covalent bonding, hydrogen bonding, electrostatic attraction, London forces, and hydrophobic interactions. The surface-modified nanoparticles are selected so that the foam composition is free of a degree of particle agglomeration or aggregation that would interfere with the desired properties of the composition, including the ability of the composition to foam.

[0031] The surface-modified nanoparticles useful in the foam compositions and methods of the present disclosure may be selected to be compatible with the vehicle to be foamed. For vehicles comprising multiple components, the surface-modified nanoparticles may be selected to be compatible with at least one component of the vehicle. For transparent vehicles, a useful method for evaluating the compatibility of surface-modified nanoparticles with transparent vehicles includes mixing the surface-modified nanoparticles with the vehicle and observing whether the surface-modified nanoparticles appear to be dissolved in the vehicle so that the resulting composition is transparent. The nature of the inorganic particle component of the surface-modified particles will prevent the surface-modified nanoparticles from actually dissolving in the vehicle, i.e., the surface-modified nanoparticles will be dispersed in the vehicle; however, the compatibility of the surface groups with the gelling agent will give the surface-modified nanoparticles the appearance of being dissolved in the vehicle. As the size of the surface-modified nanoparticles increases, the haze of the vehicle generally increases. The surface-modified nanoparticles are selected so that they do not precipitate out of the vehicle.

[0032] The surface-modified nanoparticles useful in the foam compositions and methods of the present disclosure have surface groups that alter the solubility characteristics of the nanoparticles. The surface groups are selected to make the particles compatible with a vehicle or at least one component of the vehicle in which the particles are placed so that the resulting composition forms a durable foam when foamed. When the composition is capable of polymerization, for example, the surface groups may be selected to associate or react with at least one component of the vehicle to become part of the polymer network of the composition.

[0033] Suitable surface groups can also be selected based on the solubility parameters of the surface groups and the vehicle. The surface groups or agents derived from the surface groups can be selected to have a solubility parameter similar to the solubility parameter of the vehicle to be foamed. For example, when the vehicle to be foamed is hydrophobic, one skilled in the art can select from a variety of hydrophobic surface groups to obtain surface-modified particles that are compatible with the hydrophobic vehicle. Similarly, when the vehicle to be foamed is hydrophilic, one skilled in the art can select from hydrophilic surface groups. The particles can also include at least two different surface groups that combine to provide particles having a solubility parameter similar to the solubility parameter of the vehicle.

[0034] Surface groups can be selected to provide statistically average, random surface-modified nanoparticles. Surface groups are present on the nanoparticle surface in an amount sufficient to provide surface-modified nanoparticles that can then be dispersed in a vehicle without aggregation. Surface groups can be present in an amount sufficient to form a monolayer (in some embodiments, a continuous monolayer) on the nanoparticle surface.

[0035] The surface modification group can be derived from a surface modifier. Schematically, the surface modifier can be represented by formula AB, wherein the A group can be attached to the nanoparticle surface, and the B group is a compatibilizing group that can react or not react with other components of a vehicle or composition. The compatibilizing group can be selected to make the nanoparticles relatively more polar than the nanoparticles before the treatment, relatively lower or relatively non-polar than the polarity of the nanoparticles before the treatment. In some embodiments, B is an alkyl, alkenyl, arylalkyl subunit, alkyl aromatic subunit or aryl, wherein the alkyl, alkenyl, arylalkyl subunit, alkyl aromatic subunit and aryl are optionally inserted by the following groups: at least one ether, thioether, amine, amide, ester, thioester, carbonate, thiocarbonate, carbamate, thiocarbamate, urea, thiourea or a combination thereof, and optionally end-capped by the following groups: acrylate group, methacrylate group, acrylamide group, methacrylamide group, styryl group or terminal alkenyl group (e.g., vinyl). In some embodiments, A is a hydroxyl group (e.g., -OH), a sulfonic acid group (i.e., -SO3M), a phosphonic acid group (i.e., -PO3M), a carboxylic acid group (-CO2M), an amino group (-NH2 or -N(H)alkyl), an epoxy group, or a silane group (-Si(Y) x (Z) 3-x For any of the embodiments in which W is an acid group (e.g., a carboxylic acid, a sulfonic acid, or a phosphonic acid), M is hydrogen, a free anion, or a counter cation. Examples of useful counter cations include alkali metal ions (e.g., sodium, potassium, and lithium), alkaline earth metal ions (e.g., calcium and magnesium), ammonium, and alkylammonium (e.g., dialkylammonium, trialkylammonium, and tetraalkylammonium, wherein the alkyl groups are optionally substituted with hydroxyl, fluorine, or aryl groups). For example, when the acid has an ionic interaction with the nanoparticle surface, free anions on the acid group are possible, as described in further detail below. For A is a silane (-Si(Y) x (Z) 3-x ), each Y is independently a non-hydrolyzable group (e.g., any of the R groups described below), each Z is independently a halogen (i.e., fluorine, chlorine, bromine, or iodine), a hydroxyl (i.e., —OH), an alkoxy (e.g., —O-alkyl), an aryloxy (e.g., —O-aryl), or an acyloxy (e.g., —OC(O)-alkyl), an amino (e.g., —N(R)-alkyl), an alkyl (e.g., —O-alkyl), an alkyl (e.g., —O-aryl ...alkyl), an alkyl (e.g., —O-alkyl), an alkyl (e.g., —O-aryl A )(R B ), polyalkyleneoxy; and oxime (e.g., -ON=C-(R A )(R B ), where each R A or R Balkyl), wherein alkoxy and acyloxy are optionally substituted with halogen, and aryloxy is optionally substituted with halogen, alkyl (e.g., having up to 4 carbon atoms) or haloalkyl, and x is 0 or 1. In some embodiments, alkoxy and acyloxy have up to 6 (or up to 4) carbon atoms. In some embodiments, aryloxy has 6 to 12 (or 6 to 10) carbon atoms. In some embodiments, Z can also be covalently bonded to the nanoparticle surface with -O-.

[0036] Examples of suitable types of surface modifiers include silanes, organic acids, organic bases, and alcohols. Examples of usable silanes include organosilanes, including alkylchlorosilanes, alkoxysilanes (e.g., methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, n-octyltriethoxysilane, isooctyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimeth ... isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane , polytriethoxysilane, vinyltrimethoxysilane, vinyldimethylethoxysilane, vinyltriethoxysilane, vinyldimethylethoxysilane, vinylmethyldiacetoxysilane, vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriphenoxysilane, vinyltri(tert-butoxy)silane, vinyltri(isobutoxy)silane, vinyltri(isopropenyloxy)silane and vinyltri(2-methoxyethoxy)silane); N-(3-tri- ethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate; N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate; silane-functionalized (meth)acrylates (e.g., 3-(methacryloyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-(methacryloyloxy)propyltriethoxysilane, 3-(methacryloyloxy)propylmethyldimethoxysilane, 3-(acryloxypropyl)methyldimethoxysilane, 3-(methacryloyloxy)propyl 1-(methacryloxy)propyldimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-(methacryloxy)propyldimethylethoxysilane and 3-(methacryloxy)acryltrimethoxysilane); polydialkylsiloxanes (including, for example, polydimethylsiloxane), arylsilanes (including, for example, substituted and unsubstituted arylsilanes), alkylsilanes (including, for example, substituted and unsubstituted alkylsilanes (including, for example, methoxy and hydroxy substituted alkylsilanes)) and combinations thereof. For example, methods for surface modification of silica using silane-functional (meth)acrylates are described in U.S. Pat. Nos. 4,491,508 (Olsen et al.), 4,455,205 (Olsen et al.), 4,478,876 (Chung), 4,486,504 (Chung), and 5,258,225 (Katsamberis).

[0037] Available organic acid surface modifiers include oxyacids of carbon (e.g., carboxylic acids), oxyacids of sulfur and phosphorus, and combinations thereof. Examples of polar surface modifiers with carboxylic acid functional groups include CH3O(CH2CH2O)2CH2COOH (hereinafter referred to as MEEAA) and 2-(2-methoxyethoxy)acetic acid (hereinafter referred to as MEAA) and mono(polyethylene glycol) succinate with the chemical structure CH3OCH2CH2OCH2COOH. Examples of non-polar surface modifiers with carboxylic acid functional groups include octanoic acid, dodecanoic acid, and oleic acid. Examples of suitable phosphoric acids include phosphonic acid (e.g., octylphosphonic acid, laurylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, and octadecylphosphonic acid). Available organic base surface modifiers include alkylamines (e.g., octylamine, decylamine, dodecylamine, and octadecylamine). Examples of suitable surface-modifying alcohols include aliphatic alcohols (e.g., octadecyl alcohol, dodecanol, lauryl alcohol, and furfuryl alcohol), alicyclic alcohols (such as cyclohexanol), and aromatic alcohols (e.g., phenol, benzyl alcohol), and combinations thereof. Examples of other useful non-silane surface modifiers include acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, succinic acid mono-2-(methacryloyloxyethyl) ester, and combinations thereof. A useful surface modifier that imparts polar properties and reactivity to nanoparticles is mono(methacryloyloxypolyethylene glycol) succinate.

[0038] When the vehicle includes an epoxy resin containing an aromatic ring, useful surface modifying groups may include aromatic rings. Examples of surface modifying groups particularly suitable for epoxy resin compositions are disclosed in US Pat. No. 5,648,407 (Goetz et al.).

[0039] A variety of methods for modifying the surface of nanoparticles can be used, including adding a surface modifier (e.g., in the form of a powder or colloidal dispersion) to the nanoparticles and reacting the surface modifier with the nanoparticles. Other surface modification methods that can be used are described in, for example, U.S. Pat. Nos. 2,801,185 (Iler) and 4,522,958 (Das et al.).

[0040] In some embodiments, nanoparticles that can be used for practicing the present disclosure are inorganic. The example of suitable inorganic nanoparticles includes silicon dioxide and metal oxide nanoparticles, including zirconium oxide, titanium dioxide, cerium dioxide, aluminum oxide, iron oxide, vanadium oxide, antimony oxide, tin oxide, aluminum oxide / silicon dioxide and their combination. The average particle diameter of nanoparticles is not more than 100nm, is not more than 50nm in some embodiments, and is 3nm to 100nm, 3nm to 50nm, 3nm to 20nm or 5nm to 10nm in some embodiments. If nanoparticles gather, the maximum cross-sectional size of the particles gathered is within any one of these scopes.

[0041] In some embodiments, the surface modified zirconium oxide nanoparticles include a combination of oleic acid and acrylic acid adsorbed onto the particle surface. Useful surface modified silica nanoparticles include silica nanoparticles surface modified with silane surface modifiers such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, and combinations thereof. The silica nanoparticles may be treated with a variety of surface modifiers including alcohols, organosilanes such as any of the surface modifiers described above, and combinations thereof, and organotitanates and mixtures thereof.

[0042] The nanoparticles may be in the form of a colloidal dispersion. Examples of useful commercially available unmodified silica starting materials include nano-sized colloidal silica available from Nalco Chemical Co., Naperville, IL, under the product names NALCO 1040, 1050, 1060, 2326, 2327, and 2329 colloidal silica. Useful metal oxide colloidal dispersions include colloidal zirconium oxide, suitable examples of which are described in U.S. Pat. No. 5,037,579 (Matchett); and colloidal titanium oxide, useful examples of which are described in U.S. Pat. No. 6,329,058 (Arney et al.).

[0043] In some embodiments, nanoparticles useful in practicing the present disclosure are organic. Specific examples of useful surface-modified organic molecules include alkylated buckminster fullerene (fullerene) and alkylated polyamidoamine (PAMAM)-like macromolecules. Specific examples of fullerenes include C 60 , C 70 , C 82 and C 84 Specific examples of PAMAM dendrimers include those of generations 2 to 10 (G2 to G10) available from Millipore Sigma, St. Louis, Missouri. Currently commercially available PAMAM dendrimers have primary amines, hydroxyls, sodium carboxylates, mixed amine / hydroxyls, and C 12 Surface functional groups. The alkyl groups on the organic molecules can be straight chain or branched and can be at least C3 to no more than C 30 range, and can be C3 and C 30 For example, the range can be C3 to C 22 ; C3 to C 18 ; C3 to C 12; or C3 to C8, and any combination or integer therebetween.

[0044] Another example of suitable organic nanoparticles is polymer microspheres. Specific examples of available organic polymer microspheres include microspheres comprising polystyrene as a powder or dispersion (derived from Bangs Laboratories, Inc. (Fishers, Ind.) in Fishers, Indiana). The average particle size of the polystyrene microspheres is in the range of at least 20 nm to no more than 60 nm. The average particle size currently available commercially is 20, 30, 50 and 60 nm.

[0045] A variety of methods can be used to combine the surface-modified nanoparticles and the vehicle. For example, a colloidal dispersion of the surface-modified nanoparticles can be combined with a vehicle. The solvent in the composition is then removed, leaving the surface-modified nanoparticles dispersed in the vehicle. The solvent can be removed by evaporation (e.g., distillation, rotary evaporation, or oven drying). Optionally, for some colloidal dispersions (such as aqueous colloidal dispersions), a cosolvent (e.g., methoxy-2-propanol or N-methylpyrrolidone) can be added to the colloidal dispersion before adding the vehicle to help remove water. The vehicle is added, and the water and cosolvent are removed.

[0046] Another method of adding the colloidal dispersion of surface-modified nanoparticles to a vehicle comprises drying the colloidal dispersion of surface-modified nanoparticles to a powder, and then adding a vehicle or at least one component of the vehicle to disperse the nanoparticles therein. The drying step can be accomplished using conventional means, such as oven drying or spray drying. The surface-modified nanoparticles can be designed to have a sufficient amount of surface groups to prevent irreversible agglomeration or irreversible aggregation during drying. For nanoparticles with a surface coverage of less than 100%, the drying time and drying temperature can be minimized.

[0047] The surface-modified nanoparticles can be added to the vehicle in any amount sufficient to provide a composition capable of foaming, and in some embodiments, can be added to the vehicle in any amount sufficient to provide a composition capable of forming a persistent foam. In some embodiments, the surface-modified nanoparticles are present in the foam composition in a range of 0.1% to 10% by weight based on the total weight of the foam composition. In some embodiments, the surface-modified nanoparticles are present in the foam composition in a range of 0.1% to 5% by weight, or in a range of 0.5% to 3% by weight based on the total weight of the foam composition. The surface-modified nanoparticles can be present in the foam composition in an amount of at least 0.1, 0.2, 0.3, 0.4, or 0.5% by weight and up to 10, 5, 4, or 3% by weight based on the total weight of the foam composition. In some embodiments, the surface-modified nanoparticles are dispersed throughout the vehicle, and in some embodiments, uniformly dispersed throughout the vehicle.

[0048] In some embodiments, the foam composition of the present disclosure or the foam composition made by the method of the present disclosure comprises a silicone MQ resin. The silicone MQ resin is an organosilicon polymer made of structural units called M units and Q units, the M unit being 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.

[0049]

[0050] 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.

[0051] 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. 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.

[0052] 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.

[0053] 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 of its embodiments. 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). The silicone MQ resin contains additional groups with formula -Si(R)3 after end-capping, wherein R is defined above in any embodiment of its embodiments, independent of other R groups in the silicone MQ resin. In some embodiments, the hydroxyl content of the silicone MQ resin is in the range of 185 milliequivalents / kg to 1840 milliequivalents / kg (meq / kg). In some embodiments, the hydroxyl content of the silicone MQ resin is in the range of 500 milliequivalents / kg to 1000 milliequivalents / kg (meq / kg). For the purposes of the present disclosure, the hydroxyl content is determined by NMR spectroscopy using the method for determining the MQ ratio described in the following examples.

[0054] 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.

[0055] 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.

[0056] In some embodiments, the foam composition of the present disclosure or the foam composition made by the method of the present disclosure comprises a polyoxyalkylene-modified polydimethylsiloxane. Polydimethylsiloxane is an organosilicon polymer made of a structural unit called a D unit, which is composed 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:

[0057] 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:

[0058] or a combination thereof, 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, wherein each is optionally subjected to at least one of insertion or end-capping by at least one of an ether (i.e., -O-), a thioether (i.e., -S-), an 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). 4 is methyl or hydrogen. The phrase "interrupted by at least one functional group" means having a portion of an alkylene, arylalkylene, or alkylarylene group on either side of the functional group. An example of an alkylene group interposed by an ether is -CH2-CH2-O-CH2-CH2-. Similarly, an alkylene group interposed 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 2are independently -OCH2CH2-, -OCH(CH3)CH2-, -OCH2CH2CH2-, -OCH2CH(CH3)-, -OCH2CH2CH2CH2-, -OCH(CH2CH3)CH2-, -OCH2CH(CH2CH3)-, -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 R 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.

[0059] In some embodiments, the polyoxyalkylene-modified polydimethylsiloxane useful in the foam composition of the present disclosure may be represented by Formula IV:

[0060]

[0061] 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.

[0062] 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.

[0063] In some embodiments, the silicone MQ resin, polyoxyalkylene modified polydimethylsiloxane or a combination thereof 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, polyoxyalkylene modified polydimethylsiloxane or a combination thereof is present in the foam composition in a range of 0.1 wt % to 5 wt %, or a range of 0.5 wt % to 3 wt % based on the total weight of the foam composition. The silicone MQ resin, polyoxyalkylene modified polydimethylsiloxane or a combination thereof 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. Advantageously, when the silicone MQ resin, polyoxyalkylene modified polydimethylsiloxane or a combination thereof is used in combination with surface modified nanoparticles, a lower amount of the silicone MQ resin, polyoxyalkylene modified polydimethylsiloxane or a combination thereof may be used to increase the foam height and / or stabilize the foam composition. In some embodiments, the foam composition is free of fluorinated surfactants.

[0064] The vehicle of the foam composition can include multiple components, and can be in the form of solid, liquid or their combination. 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 is an organic liquid. The available example of an organic liquid includes acid, alcohol, ketone, aldehyde, amine, ether, hydrocarbon, halogenated hydrocarbon, monomer, oligomer and polymer.

[0065] In some embodiments, the vehicle includes water. In some embodiments, the vehicle excludes water. In some embodiments, the foam composition comprises no greater than 50%, 40%, 30%, 20%, 10%, 5%, or 1% by weight water.

[0066] 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 elastomer, ethylene-propylene rubber, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-butylene-styrene rubber, styrene-ethylene-propylene-styrene rubber, polyisobutylene rubber, ethylene vinyl acetate rubber, silicone rubber (e.g., polysiloxane), polymethacrylate rubber, polyacrylate rubber (e.g., copolymer of isooctyl acrylate and acrylic acid), polyester, polyether ester, polyvinyl ether, polyurethane and blends and copolymers thereof. Useful copolymers include linear block copolymers, radial block copolymers, star block copolymers and tapered block copolymers and combinations thereof.

[0067] 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.

[0068] 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.

[0069] 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, acrylated oils, and acrylated polyesters.

[0043] The invention also includes but is not limited to olefins, olefins, and oligomers. The invention also includes but is not limited to olefins, olefins, and oligomers. The invention also includes but is not limited to olefins, olefins, and oligomers. The invention also includes but is not limited to olefins, olefins, and oligomers.

[0070] 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.

[0071] In some embodiments, the vehicle is not a silicone polymer. In some embodiments, the vehicle comprises an organic polymer other than a silicone-containing polymer. In some embodiments, the vehicle comprises an organic polymer other than an acrylated silicone, a silicone-containing polyurethane, or an epoxy / silicone resin.

[0072] Can select vehicle to provide adhesive composition, including pressure-sensitive adhesive composition, hot melt adhesive composition, thermosetting adhesive composition and thermoplastic adhesive composition.This vehicle can include any pressure-sensitive adhesive composition, including solvent-coated adhesive, hot melt-coated adhesive, radiation-curable adhesive (for example, with electron beam, actinic radiation such as visible light and UV and heat), water-based adhesive (for example, emulsion) and their combination.Pressure-sensitive adhesive (PSA) composition suitable for vehicle includes tackifying rubber adhesive (for example, natural rubber, olefin, silicone, polyisoprene, polybutadiene, polyurethane, styrene-isoprene-styrene and styrene-butadiene-styrene block copolymer and other elastomer), and tackifying and non-tackifying acrylic adhesive composition.In some embodiments, this PSA composition is not and / or does not include silicone rubber.

[0073] In some embodiments, the vehicle comprises at least one of an organic polymer or an organic monomer. In some embodiments, the vehicle comprises an organic polymer and an organic monomer for making the organic polymer.

[0074] In some embodiments, the vehicle comprises an acrylic PSA or a precursor thereof (e.g., a first acrylic monomer and optionally a second acrylic monomer). In some embodiments, the vehicle comprises a copolymer of an alkyl ester of acrylic acid as a first monomer and optionally a small 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:

[0075] CH2=C(R 5 )COOR 6 (V)

[0076] 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):

[0077]

[0078] 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 7and R 8 The 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.).

[0079] 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 PSA 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-butylamino acrylate, 4 ... 4-hydroxymethylcyclohexyl)methyl acrylate, dimethylaminoethyl acrylate, tert-butylamino acrylate, 4-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxy

[0063] The invention also includes but is not limited to 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.

[0080] 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.

[0081] 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.

[0082] The vehicle can include any of these monomers, a polymer made from any of these monomers, or a combination thereof.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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).

[0088] 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). ;

[0089] 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.

[0090] 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., the first acrylic monomer and the 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% by weight, 80% by weight, 85% by weight, 90% by weight, 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.

[0091] 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).

[0092] 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.

[0093] 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.

[0094] 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.).

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] In some embodiments, the vehicle includes a silane coupling agent. Examples of available silane coupling agents include many of the silanes listed above that can be used to treat nanoparticles, as well as epoxysilanes, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethoxydimethoxysilane, and 3-glycidoxypropylmethoxytriethoxysilane; 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 may 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.

[0100] 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.

[0101] Examples of chemical foaming agents include water, azo molecules, carbonate (or ester) molecules, and hydrazide 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 acid, oxalic acid hydrazide, 1,2-hydrazonocarboxylate (or ester), diphenyl ether-4,4'-disulfonylhydrazide, tetrazole compounds, sodium bicarbonate, ammonium bicarbonate, carbonate (or ester) compounds, and preparations of polycarbonic acid, mixtures of citric acid and sodium bicarbonate, N,N'-dimethyl-N,N'-dinitroso-terephthalamide, N,N'-dinitrosopentamethylenetetramine, and combinations thereof). Water is a foaming agent that can be used to make polyurethane foam. Water reacts with isocyanate to eventually form carbon dioxide, which causes polyurethane to foam.

[0102] Suitable inorganic physical blowing agents include, for example, nitrogen, argon, oxygen, water, air, helium, sulfur hexafluoride, and combinations thereof.

[0103] 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.

[0104] 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, Fluorocyclobutane, 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-222-trifluoroethane (HCFC-123) and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124), trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane and combinations thereof. In some embodiments, the blowing agent is unhalogenated. In some embodiments, the blowing agent is unfluorinated.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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 placing about 30 grams of a 1% by weight solution of a blend of surface-modified nanoparticles and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane in a 4-ounce glass jar containing a vehicle, and bubbling nitrogen through the mixture for five minutes at 22°C using the apparatus described in the slurry bubbling test in the examples while stirring the mixture with a magnetic stir bar set at a low setting. Stop bubbling and turn off the magnetic stir bar. Measure the foam height with a ruler. Measure the time required for half of the liquid to be drained from the foam (i.e., to provide half of the initial volume of liquid) to provide the foam half-life.

[0109] As shown in the comparison of Examples 1 to 6 with Comparative Example 1 below, silicone MQ resins, which are reported to be defoamers or antifoaming agents, do not adversely affect the foaming ability of surface-modified nanoparticles in the vehicle of acrylic monomers. In fact, silicone MQ resins were shown to enhance the foaming ability of the surface-modified nanoparticles in Examples 1 to 3. In addition, silicone MQ resins were found to be compatible with surface-modified nanoparticles and did not cause gelation or inhomogeneity when mixed together. As shown in the comparison of Examples 7, 8 and 10 with Comparative Examples 2 and Comparative Examples 4 below, compositions comprising surface-modified nanoparticles and polyoxyalkylene-modified polydimethylsiloxanes have a surprising synergistic effect, wherein the combination is more capable of foaming and forming a durable foam than compositions comprising only surface-modified nanoparticles or polyoxyalkylene-modified polydimethylsiloxanes. Examples 7 and 8 foam better than Example 9 and form a more durable foam. The polyoxyalkylene-modified polydimethylsiloxanes used in Examples 7 and 8 contained vinyloxy groups, and the polyoxyalkylene-modified polydimethylsiloxane used in Example 9 contained a combination of vinyloxy groups and propyleneoxy groups, except that the number average molecular weight was not greater than 10,000 g / mol.

[0110] 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 to form voids in the composition, the composition comprising a vehicle, surface-modified nanoparticles having a particle size not greater than 100 nanometers, and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane. The foaming agent can be any of the above-mentioned chemical or physical foaming agents. In some embodiments, after the surface-modified nanoparticles have been dispersed throughout the vehicle, the composition is foamed, and in some embodiments, uniformly dispersed throughout the vehicle. The composition can be foamed according to a variety of foaming methods (including, for example, the foaming methods described in U.S. Pat. Nos. 5,024,880 (Vesley et al.), 4,895,745 (Vesley et al.), and 4,748,061 (Vesley et al.)).

[0111] 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.

[0112] 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).

[0113] The foam composition can also be formulated for use in applications such as foaming personal care products, including, for example, hair treatment compositions, shaving compositions, and skin treatment compositions; medical applications, including bandages and wound dressings; and household and industrial applications, including cups, plates, ear plugs, cushions, pillows, insulation, dampers (e.g., for suppressing sound, absorbing vibrations (e.g., cushioning hood vibrations)), and combinations thereof, and baffles.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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 .

[0118] 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.

[0119] 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.

[0120] The foam composition may also be subjected to post-processing including, for example, die cutting, cross-linking, and sterilization.

[0121] Some embodiments of the present disclosure

[0122] In a first embodiment, the present disclosure provides a foam composition comprising: a vehicle, surface-modified nanoparticles having a particle size of no more than 100 nanometers, and at least one of a silicone MQ resin or a polyoxyalkylene-modified polydimethylsiloxane. In a second embodiment, the present disclosure provides a foam composition according to the first embodiment, wherein the foam composition comprises the silicone MQ resin. In a third embodiment, the present disclosure provides a foam composition, wherein the foam composition comprises: a vehicle, surface-modified nanoparticles having a particle size of no more than 100 nanometers, and a silicone MQ resin. 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 at least 0.8:1, 0.9:1, 1:1, 1.1:1, or 1.2:1. In a fifth embodiment, the present disclosure provides a foam composition according to any one of the first to fourth embodiments, wherein the silicone MQ resin has an M:Q ratio of no more than 2.5:1 or 2:1. 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 is prepared 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 heterocyclic group, wherein the alkyl and alkylene group subjected to at least one of insertion or end-capping by arylene group or heterocyclic group are unsubstituted or substituted by halogen and are optionally substituted by at least one of -O-, -NR'-,

[0123] -S-, -Si- or a combination thereof, and wherein the aryl, arylidene and heterocyclylene are unsubstituted or substituted with at least one alkyl, alkoxy, halogen or a combination thereof, and wherein each R 1R 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 seventh embodiment, the present disclosure provides a foam composition according to any one of the first to sixth embodiments, wherein the silicone MQ resin comprises a methyl group. In an eighth embodiment, the present disclosure provides a foam composition according to any one of the first to seventh embodiments, wherein the hydroxyl content of the silicone MQ resin is in the range of 185 milliequivalents / kg to 1840 milliequivalents / kg. In a ninth embodiment, the present disclosure provides a foam composition according to any one of the first to eighth embodiments, wherein the foam composition comprises or further comprises a polyoxyalkylene-modified polydimethylsiloxane. In a tenth embodiment, the present disclosure provides a foam composition according to the first or ninth embodiment, wherein the polyoxyalkylene-modified polydimethylsiloxane comprises a repeating divalent unit represented by formula II:

[0124] 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:

[0125] 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, each of the groups is optionally subjected to at least one of insertion or end-capping by at least one of an ether, a thioether, an amine, an amide, an ester, a thioester, a carbonate, a thiocarbonate, a carbamate, a thiocarbamate, a urea, or a 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 3is hydrogen, alkyl, acyl, aryl or arylalkylene, wherein aryl and arylalkylene are unsubstituted or substituted with at least one alkyl, alkoxy or combination thereof. In an eleventh embodiment, the present disclosure provides a foam composition according to the first, ninth or tenth embodiment, wherein the number average molecular weight of the polyoxyalkylene-modified polydimethylsiloxane is no greater than 50,000 g / mol, 40,000 g / mol, 30,000 g / mol, 20,000 g / mol or 10,000 g / mol. In a twelfth embodiment, the present disclosure provides a foam composition according to any one of the first or ninth to eleventh embodiments, wherein the polyoxyalkylene-modified polydimethylsiloxane comprises ethyleneoxy groups, propyleneoxy groups or combinations thereof. In a thirteenth embodiment, the present disclosure provides a foam composition according to any one of the first to twelfth embodiments, wherein the silicone MQ resin, the polyoxyalkylene-modified polydimethylsiloxane, or a combination thereof 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.

[0126] In the fourteenth embodiment, the present disclosure provides a foam composition according to any one of the first to twelfth embodiments, wherein the vehicle comprises at least one of a monomer or a polymer or a combination thereof. In the fifteenth embodiment, the present disclosure provides a foam composition according to any one of the first to fourteenth embodiments, wherein the vehicle is not silicone or a silicone-containing polymer. In the sixteenth embodiment, the present disclosure provides a foam composition according to any one of the first to fifteenth embodiments, wherein the vehicle comprises at least one of a thermoplastic polymer, a thermosetting polymer, or an elastomer. 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 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 eighteenth embodiment, the present disclosure provides a foam composition according to any one of the first to seventeenth embodiments, wherein the vehicle comprises a cross-linked 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 at least one of an acrylate or an acrylic polymer. In a 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 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 formula (VI):

[0127]

[0128] 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 3A polymer of a unit containing hydrogen or a methyl group, or any of these groups. 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 includes acrylic acid and at least one of isooctyl acrylate or 2-ethylhexyl acrylate. In the twenty-second embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-first embodiments, wherein the vehicle includes a polyolefin. In the twenty-third embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-second embodiments, wherein the vehicle includes at least one of a novolac resin, a resol phenolic resin, or a polyurea resin. In the twenty-fourth embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-third embodiments, wherein the vehicle includes at least one of an isocyanate, a polyurethane, or a polyurea. In the twenty-fifth embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-fourth embodiments, 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.

[0129] In the twenty-sixth embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-fifth embodiments, wherein the vehicle has voids therein. In the twenty-seventh embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-sixth embodiments, the foam composition further comprising a foaming agent. In the twenty-eighth embodiment, the present disclosure provides a foam composition according to the twenty-seventh embodiment, wherein the foaming agent comprises 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 half-life of the foam composition at 22° C. being at least 10 minutes. In the thirtieth embodiment, the present disclosure provides a foam composition according to any one of the first to twenty-ninth embodiments, the foam composition further comprising at least one of fumed silica, hollow ceramic microspheres, or hollow polymer microspheres.

[0130] In a thirty-first embodiment, the present disclosure provides a foam composition according to any one of the first to thirtieth embodiments, wherein the particle size of the surface-modified nanoparticles is no greater than about 50 nanometers. In a thirty-second embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-first embodiments, wherein the surface-modified nanoparticles comprise inorganic nanoparticles. In a thirty-third embodiment, the present disclosure provides a foam composition according to the thirty-second embodiment, wherein the surface-modified nanoparticles comprise at least one of silica, titania, alumina, zirconium oxide, vanadium oxide, cerium dioxide, iron oxide, antimony oxide, tin oxide, or aluminum / silicon dioxide. In a thirty-fourth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-first embodiments, wherein the surface-modified nanoparticles comprise organic nanoparticles. In a thirty-fifth embodiment, the present disclosure provides a foam composition according to the thirty-fourth embodiment, wherein the surface-modified nanoparticles comprise at least one of alkylated buckminster fullerene or alkylated polyamidoamine dendrimers. In a thirty-sixth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-fifth embodiments, wherein the surface-modified nanoparticles comprise hydrophobic surface groups, hydrophilic surface groups, or a combination thereof. In a thirty-seventh embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-sixth embodiments, wherein the surface-modified nanoparticles comprise surface groups derived from organosilanes, organic acids, organic bases, or a combination thereof. In a thirty-eighth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-seventh embodiments, wherein the surface-modified nanoparticles comprise surface groups derived from organosilanes, carboxylic acids, sulfonic acids, phosphonic acids, or a combination thereof. In a thirty-ninth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-eighth embodiments, wherein the surface-modified nanoparticles are 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 3 wt %, based on the total weight of the foam composition. In a fortieth embodiment, the present disclosure provides a foam composition according to any one of the first to thirty-ninth embodiments, wherein the foam composition does not contain a fluorinated surfactant.

[0131] In the forty-first embodiment, the present disclosure provides a foam composition according to any one of the first to fortieth embodiments, wherein the vehicle comprises an adhesive composition. In the forty-second embodiment, the present disclosure provides a foam composition according to the forty-first embodiment, wherein the vehicle comprises a pressure-sensitive adhesive composition. In the forty-third embodiment, the present disclosure provides a foam composition according to the forty-first embodiment, wherein the vehicle comprises a hot melt adhesive composition. In the forty-fourth embodiment, the present disclosure provides an adhesive tape comprising the foam composition according to any one of the forty-first to forty-third embodiments. In the forty-fifth embodiment, the present disclosure provides an article comprising the foam composition according to any one of the first to forty-third embodiments.

[0132] In the forty-sixth embodiment, the present disclosure provides a method for making an adhesive tape according to the forty-fourth embodiment, the method comprising applying the foam composition to a substrate. In the forty-seventh embodiment, the present disclosure provides a method according to the forty-sixth embodiment, wherein the vehicle comprises a monomer and an optional polymer, and the method further comprises polymerizing the monomer. In the forty-eighth embodiment, the present disclosure provides a method according to the forty-sixth embodiment or the forty-seventh embodiment, the method further comprises crosslinking the foam composition. In the forty-ninth embodiment, the present disclosure provides a method for making a foam composition according to any one of the first to forty-third embodiments, the method comprising introducing a foaming agent into the composition to form voids in the composition, the composition comprising the vehicle, the surface-modified nanoparticles having a particle size not greater than 100 nanometers, and at least one of the silicone MQ resin or the polyoxyalkylene-modified polydimethylsiloxane. In the fiftieth embodiment, the present disclosure provides a method according to the forty-ninth embodiment, wherein the introduction of the foaming agent comprises at least one of stirring the composition or injecting a gas into the composition. In a fifty-first embodiment, the present disclosure provides a method according to the fiftieth embodiment, wherein the blowing agent comprises at least one of air, nitrogen, oxygen, carbon dioxide, helium, argon, or nitrous oxide.

[0133] The following specific, non-limiting examples will serve to illustrate the present disclosure.

[0134] Example

[0135] 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 = liters per minute, mM = millimole, mm = milliliter, mL = milliliter, NMR = nuclear magnetic resonance, and wt% = weight percent. The materials used in the examples and their sources are shown in Table 1 below.

[0136] Table 1. Materials list

[0137]

[0138] M:Q ratio determination

[0139] 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.

[0140] Determination of Molecular Weight of Polydimethylsiloxane Modified with Polyoxyalkylene

[0141] 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 was used to determine the number average molecular weight. The data are shown in Table 4 below.

[0142] Preparation of surface-modified nanoparticles

[0143] 350g of aqueous colloidal silica dispersion "NALCO 2326" was charged into a 1-liter 3-necked round-bottom flask and stirring was started. Then 222g of 2-propanol was slowly added. A small amount of exotherm was observed. After mixing for about 10 minutes, 25.6g of n-octyltrimethoxysilane was added, followed by 2.6g of methyltrimethoxysilane and rinsed with 19g of 2-propanol. The mixture was heated to 82°C. The mixture became a thick white slurry at about 80°C. The mixture was kept at 82°C for 4 hours and then cooled to 25°C. The mixture was transferred to a 1-neck pear-shaped flask and rinsed with about 120g of 2-propanol. The solvent was removed by rotary evaporation (bath temperature 50°C), and the vacuum was slowly reduced to 80mmHg). About 370g of distillate was removed, and the mixture was cooled to 25°C. 80.0g of 2-EHA and 0.02g of phenothiazine were added to the mixture. The mixture was subjected to rotary evaporation (initial bath temperature 35°C and increased to 50°C, vacuum slowly reduced to 19 mmHg) to remove any residual solvent and water. The material turned from cloudy to clear as the water was removed. 149.1 g of the resulting product, 50 wt% surface-modified nanoparticles in 2-EHA, was transferred from the flask to a wide-mouth bottle.

[0144] Examples 1 to 10 (EX 1 to EX 10) and Comparative Examples (CE 1 to CE 4)

[0145] In a tall glass sample vial, 0.20 g of a 70:30 mixture of surface modified nanoparticles (50 wt % in 2-EHA) and silicone MQ resin or polyoxyalkylene modified polydimethylsiloxane (as shown in Table 4 below) was weighed and added to EX 1 to EX10. For CE 1, only 0.20 g of surface modified nanoparticles (50 wt % in 2-EHA) was added. For CE 2 to CE 4, only 0.20 g of polyoxyalkylene modified polydimethylsiloxane shown in Table 4 below was added. For Examples 3 and 4, 0.1 g of 2-EHA was added. For Examples 7 to 9, 0.06 g of 2-EHA was added because the samples gelled without the addition of 2-EHA. 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 vials were capped and evaluated using the foam column screening test described below. The data is shown in Table 4 below.

[0146] Foam column screening test (manual agitation)

[0147] The prepared samples containing the acrylic monomer mixtures of Examples 1 to 10 and Comparative Examples CE 1 to CE 4 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 to be provided) was measured and recorded as the foam half-life. The overall evaluation is further described in Table 2 below.

[0148] Table 2: Overall evaluation of foam height and foam persistence

[0149]

[0150] Examples 1A to 10A (EX 1A to EX 10A) and Comparative Examples (CE 1A to CE 4A) for Slurry Bubble Testing

[0151] 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.

[0152] In a 4 ounce glass jar equipped with a magnetic stir bar, 30.0 g of the slurry was weighed. Then 0.30 g of a 70:30 mixture of surface-modified nanoparticles (50 wt % in 2-EHA) and silicone MQ resin or polyoxyalkylene-modified polydimethylsiloxane (as shown in Table 4 below) was added to the glass jar for EX 1A to EX10A. For CE 1A, only 0.30 g of surface-modified nanoparticles (50 wt % in 2-EHA) was added. For CE 2A to CE 4A, only 0.30 g of polyoxyalkylene-modified polydimethylsiloxane shown in Table 4 below was added. For Examples 3 and 4, 0.15 g of 2-EHA was added. For Examples 7 to 9, 0.09 g of 2-EHA was added. The samples were then capped. The samples were stirred on a magnetic stir plate for five minutes and then subjected to the slurry bubble test described below. The data is shown in Table 4 below.

[0153] Slurry Bubble Test

[0154] Set up a bubbling apparatus. Connect the room 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 apparatus bubble for five minutes. Then remove the needle and turn off the magnetic stir bar. Then re-cover the glass jar lid and let the glass jar be at surface level.

[0155] 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.

[0156] Table 3: Foam height and foam persistence for slurry bubbling test

[0157]

[0158] na = not applicable because so little foam is produced

[0159] Table 4: Examples EX 1-EX 10 and Examples EX1A-EX-10A and Comparative Examples CE 1 to CE 4 and Comparative Example CE 1A to CE 4A Composition and Results

[0160]

[0161] a SMN = surface modified nanoparticles b nd = not determined c na = not applicable

[0162] 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.

Claims

1. A foam composition, comprising: a medium having a void therein; Surface-modified nanoparticles having a particle size of 100 nanometers or less; and At least one of silicone MQ resin or polyoxyalkylene-modified polydimethylsiloxane.

2. The foam composition according to claim 1, wherein the foam composition comprises the silicone MQ resin.

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

1.

4. The foam composition of claim 2 or 3, 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.

5. The foam composition of any one of claims 1 to 4, wherein the foam composition comprises a polyoxyalkylene-modified polydimethylsiloxane having a number average molecular weight of no more than 50,000 g / mole, 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, wherein the silicone MQ resin, the polyoxyalkylene-modified polydimethylsiloxane or a combination thereof is present in the foam composition in an amount of 0.1 wt% to 10 wt% based on the total weight of the foam composition.

7. The foam composition of any one of claims 1 to 6, wherein the vehicle comprises at least one of a polymer or a monomer.

8. The foam composition of any one of claims 1 to 7, wherein the vehicle is not silicone or a silicone-containing polymer.

9. The foam composition of any one of claims 1 to 8, wherein the vehicle 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 surface modified nanoparticles comprise at least one of silica, titania, alumina, zirconia, vanadium oxide, ceria, iron oxide, antimony oxide, tin oxide, or aluminum / silica.

11. The foam composition of any one of claims 1 to 10, wherein the surface-modified nanoparticles comprise surface groups derived from silanes, organic acids, organic bases, or combinations thereof.

12. The foam composition of any one of claims 1 to 11, wherein the surface-modified nanoparticles are present in the foam composition in a range of 0.1 wt% to 10 wt% based on the total weight of the foam composition.

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 producing a foam composition according to any one of claims 1 to 13, the method comprising introducing a blowing agent into a composition to form voids in the composition, the composition comprising the vehicle, the surface-modified nanoparticles having a particle size of not greater than 100 nanometers, and at least one of the silicone MQ resin or the polyoxyalkylene-modified polydimethylsiloxane.

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