Acrylic-Based Adhesive Composition with Ethylene/Acid Copolymer

Abstract

The present disclosure is directed to a water-based pressure-sensitive adhesive composition. In an embodiment, the water-based pressure-sensitive adhesive composition includes (A) an acrylic dispersion composed of particles of (i) an acrylic-based polymer with a glass transition temperature (Tg) less than −20° C., and (ii) a surfactant. The water-based pressure-sensitive adhesive composition also includes (B) an ethylene acid dispersion composed of (i) particles of an ethylene acid copolymer having from 3 wt % to less than 50 wt % acid comonomer and a melt index from 1 g/10 min to 100 g/10 min, and (ii) at least one of a dispersant or a neutralizing agent. Further disclosed are articles with the water-based pressure-sensitive adhesive composition.

Claims

1. A water-based pressure-sensitive adhesive composition comprising: (A) an acrylic dispersion comprising particles of (i) an acrylic-based polymer with a glass transition temperature (Tg) less than −20° C., and (ii) a surfactant; (B) an ethylene acid dispersion comprising (i) particles of an ethylene acid copolymer having from 3 wt % to less than 50 wt % acid comonomer and a melt index from 1 g/10 min to 100 g/10 min, and (ii) at least one of a dispersant or a neutralizing agent.

2. The water-based pressure-sensitive adhesive composition of claim 1 wherein the acrylic-based polymer includes one or more acrylic-based monomers selected from the group consisting of acrylic acid (AA), butyl acrylate (BA), ethylhexyl acrylate (2-EHA), ethyl acrylate (EA), methyl acrylate (MA), butyl methacrylate (BMA), octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate (MMA), isobutyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, pentadecyl methacrylate, stearyl methacrylate, n-butyl methacrylate, C.sub.12 to C.sub.18 alkyl methacrylates, cyclohexyl methacrylate, methacrylic acid, and combinations thereof.

3. The water-based pressure-sensitive adhesive of claim 2 wherein the acrylic-based polymer includes a monomer selected from the group consisting of styrene, vinyl ester, and combinations thereof.

4. The water-based pressure-sensitive adhesive composition of claim 1 wherein the acrylic-based polymer has a Tg from −80° C. to −20° C.

5. The water-based pressure-sensitive adhesive composition of claim 1 wherein the ethylene acid copolymer is selected from the group consisting of ethylene and acrylic acid copolymer, ethylene and methacrylic acid copolymer, and combinations thereof.

6. The water-based pressure-sensitive adhesive composition of claim 5 wherein the ethylene acid copolymer is an ethylene and methacrylic acid copolymer.

7. The water-based pressure-sensitive adhesive composition of claim 5 wherein the ethylene acid copolymer is an ethylene and acrylic acid copolymer.

8. The water-based pressure-sensitive adhesive composition of claim 1 wherein the particles of the ethylene acid copolymer have a volume average particle size from 0.05 microns to 2.0 microns.

9. The water-based pressure-sensitive adhesive composition of claim 1 wherein the ethylene acid copolymer has a density from 0.920 g/cc to 0.960 g/cc; a melting point, Tm, from 70° C. to 110° C.; and a Vicat softening point from 48° C. to 95° C.

10. The water-based pressure-sensitive adhesive composition of claim 1 wherein the ethylene acid dispersion comprises composite particles composed of a first ethylene acid copolymer having from 3 wt % to 50 wt % acid comonomer, and a second ethylene acid copolymer having from 3 wt % to 50 wt % acid comonomer, the second ethylene acid copolymer different than the first ethylene acid copolymer.

11. The water-based pressure-sensitive adhesive composition of claim 1 wherein the dispersant is selected from the group consisting of a long chain fatty acid having from 14 to 40 carbon atoms, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polyethylene with acid functionality, a polypropylene with acid functionality, and combinations thereof.

12. The water-based pressure-sensitive adhesive composition of claim 1 comprising a neutralizing agent selected from the group consisting a hydroxide, a carbonate, a hydrogen carbonate, an amine, and combinations thereof.

13. The water-based pressure-sensitive adhesive composition of claim 1 comprising (A) from 40 wt % to 99.8 wt % of the acrylic dispersion; (B) from 10 wt % to 0.2 wt % of the ethylene acid dispersion; (C) from 0 wt % to 50 wt % tackifier; wherein weight percent is based on the total dry weight of the water-based pressure-sensitive adhesive composition.

14. An article comprising: a first substrate; and a layer of a water-based pressure-sensitive adhesive composition on the first substrate, the water-based pressure-sensitive adhesive composition comprising: (A) an acrylic dispersion comprising particles of (i) an acrylic-based polymer with a glass transition temperature (Tg) less than −20° C., and (ii) a surfactant; (B) an ethylene acid dispersion comprising (i) particles of an ethylene acid copolymer having from 3 wt % to less than 50 wt % acid comonomer and a melt index from 1 g/10 min to 100 g/10 min, and (ii) at least one of a dispersant or a neutralizing agent.

Description

DETAILED DESCRIPTION

[0041] The present disclosure relates to a water-based pressure-sensitive adhesive composition. In an embodiment, the water-based pressure-sensitive adhesive composition includes (A) an acrylic dispersion composed of (i) an acrylic-based polymer with a glass transition temperature (Tg) less than −20° C., and (ii) a surfactant. The water-based pressure-sensitive adhesive composition also includes (B) an ethylene acid dispersion. The ethylene acid dispersion is composed of (i) an ethylene acid copolymer and (ii) a dispersant or a neutralizing agent. The ethylene acid copolymer contains from 3 wt % to less than 50 wt % acid comonomer and has a melt index from 1 g/10 min to 100 g/10 min. The ethylene acid copolymer is in the form of particles.

A. Acrylic Dispersion

[0042] The water-based PSA composition includes an acrylic dispersion. The term “water-based PSA composition” is a pressure sensitive adhesive composition wherein water is the continuous phase, i.e., a composition having an aqueous medium. The acrylic dispersion includes one or more acrylic-based monomers, a surfactant, and water to the exclusion of an ethylene-based polymer. The surfactant acts as an emulsifier and enables droplets of the acrylic-based monomer, which is hydrophobic, to form throughout the aqueous medium. An initiator is then introduced into the emulsified mixture. The initiator reacts with the acrylic-based monomer(s) dispersed throughout the aqueous medium until all, or substantially all, of the acrylic-based monomer(s) is polymerized. The end result is an acrylic dispersion composed of a dispersion of acrylic-based polymer particles in the aqueous medium, the acrylic-based polymer particles composed of one or more acrylic-based monomer subunits to the exclusion of ethylene-based polymer.

[0043] The acrylic-based polymer has a Tg less than −20° C., or from −80° C. to −20° C., or from −70° C. to −30° C., or from −60° C. to −40° C. and a Mw from greater than 100,000 daltons to 10,000,000 daltons. Nonlimiting examples of suitable acrylic-based monomers include acrylic acid (AA), butyl acrylate (BA), ethylhexyl acrylate (2-EHA), ethyl acrylate (EA), methyl acrylate (MA), butyl methacrylate (BMA), octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate (MMA), isobutyl methacrylate, octyl methacrylate, isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, pentadecyl methacrylate, stearyl methacrylate, n-butyl methacrylate, C.sub.12 to C.sub.18 alkyl methacrylates, cyclohexyl methacrylate, methacrylic acid, and combinations thereof. In addition to acrylic-based monomer, the acrylic-based polymer may also include monomer such as 2-hydroxyethyl acrylate (2-HEA), styrene (STY), vinyl ester, vinyl acetate, and combinations thereof.

[0044] The acrylic-based dispersion includes a surfactant. Nonlimiting examples of suitable surfactant include cationic surfactants, anionic surfactants, zwitterionic surfactants, non-ionic surfactants, and combinations thereof. Examples of anionic surfactants include, but are not limited to, sulfonates, carboxylates, and phosphates. Examples of cationic surfactants include, but are not limited to, quaternary amines. Examples of non-ionic surfactants include, but are not limited to, block copolymers containing ethylene oxide and silicone surfactants, such as ethoxylated alcohol, ethoxylated fatty acid, sorbitan derivative, lanolin derivative, ethoxylated nonyl phenol, or alkoxylated polysiloxane. Commercially-available examples of suitable surfactants include, but are not limited to, surfactants sold under the trade names TERGITOL™ and DOWFAX™ by The Dow Chemical Company, such as TERGITOL™ 15-S-9 and DOWFAX™ 2A1, and products sold under the DISPONIL trade name by BASF SE, such as DISPONIL FES 77 IS and DISPONIL FES 993.

[0045] The initiator can be either a thermal initiator or a redox system initiator. Examples of the thermal initiator include, but are not limited to, ammonium persulfate, sodium persulfate, and potassium persulfate. When the initiator is a redox system initiator, the reducing agent can be, for example, an ascorbic acid, a sulfoxylate, or an erythorbic acid, while the oxidating agent can be, for example, a peroxide or a persulfate.

[0046] In an embodiment, the acrylic dispersion includes particles of an acrylic-based polymer having the following properties: [0047] (i) two or more monomer subunits selected from any combination of 2-EHA, MA, MMA, STY, 2-HEA, AA, BA, EA, VA, and BMA; and [0048] (ii) a Tg from −60° C. to −30° C.

[0049] In an embodiment, the acrylic dispersion includes particles of an acrylic-based polymer having the following properties: [0050] (i) monomer subunits of 2-EHA, EA, MMA, and AA; and [0051] (ii) a Tg from −60° C. to −30° C.

[0052] In an embodiment, the acrylic dispersion includes particles of an acrylic-based polymer having the following properties: [0053] (i) monomer subunits of 2-EHA, MMA, STY, 2-HEA, AA, and BA; and [0054] (ii) a Tg from −60° C. to −30° C.

B. Ethylene Acid Dispersion

[0055] The water-based PSA composition includes an ethylene acid dispersion. The ethylene acid dispersion includes (i) particles of an ethylene acid copolymer, (ii) a dispersant or a neutralizing agent, and (iii) water. The ethylene acid copolymer has from 3 wt % to less than 50 wt % acrylic-based comonomer, the ethylene acid copolymer having a melt index from 1 g/10 min to 100 g/10 min.

[0056] An “ethylene acid copolymer,” (interchangeably referred to as “EAC”) as used herein, includes copolymerized comonomers of (a) ethylene; (b) from 3 wt % to less than 50 wt % of at least one C.sub.3 to C.sub.8 α,β ethylenically unsaturated carboxylic acid; and, optionally, (c) from 10 wt % to 30 wt % of at least one C.sub.3 to C.sub.8 α,β ethylenically unsaturated carboxylic acid ester, based on the total weight of monomers present in the ethylene acid copolymer.

[0057] The α,β-ethylenically unsaturated C.sub.3 to C.sub.8 carboxylic acid, component (b) includes, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid (trans-butenoic acid), isocrotonic acid (cis-butenoic acid), vinylacetic acid, (E)-4-methoxy-4-oxo-but-2-enoic acid, (Z)-4-ethoxy-4-oxo-but-2-enoic acid, vinyllactic acid, maleic acid, 2-methylmaleic acid or aconitic acid; or mixtures thereof. In an embodiment, the C.sub.3 to C.sub.8 α,β ethylenically unsaturated carboxylic acid is acrylic acid, methacrylic acid, or a combination of acrylic acid and methacrylic acid.

[0058] The ethylene acid copolymer may optionally include C.sub.3 to C.sub.8 α,β ethylenically unsaturated carboxylic acid ester, component (c). When the C.sub.3 to C.sub.8 α,β ethylenically unsaturated carboxylic acid ester component (c) is present, component (c) may include monoesters or, in some examples, diesters of α,β-unsaturated dicarboxylic acids with primary, secondary and/or tertiary saturated monohydric alcohols having from 1 carbon atom to 20 carbon atoms. The acid esters may be, for example, methyl, ethyl, propyl, butyl or the 2-ethylhexyl esters of acrylic acid, of methacrylic acid and/or itaconic acid, or the corresponding monoesters or diesters of maleic acid, fumaric acid or citraconic acid.

[0059] Acrylic acid and methacrylic acid have respective Structure (II) and Structure (III) below:

##STR00002##

[0060] In an embodiment, the EAC consists of (i) ethylene, (ii) from 3 wt % to less than 50 wt % of an acrylic acid comonomer and/or a methacrylic acid comonomer, and (iii) optionally a termonomer. Nonlimiting examples of suitable termonomer include one or more C.sub.3-C.sub.8 α-olefin, vinyl acetate, esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, and butyl acrylate, and combinations thereof. When present, the amount of termonomer in the EAC is from greater than 0 wt % to less than 30%, or from 1 wt % to 10 wt %, or from 3 wt % to 8 wt %, with weight percent based on the total weight of the EAC. When the termonomer is present, it is understood the total weight percent of (i) units derived from ethylene, (ii) units derived from acrylic acid and/or methacrylic acid comonomer and (iii) units derived from the termonomer amount to 100 wt % EAC.

[0061] In an embodiment, the ethylene acid dispersion includes particles of an EAC that is an ethylene copolymer consisting of (i) ethylene and (ii) acrylic acid comonomer or methacrylic acid comonomer.

[0062] In an embodiment, the ethylene acid dispersion includes particles of an EAC consisting of (i) ethylene and (ii) acrylic acid comonomer or methacrylic acid comonomer. The EAC contains from 3 wt % to less than 50 wt %, or from 9 wt % to 30 wt %, or from 9 wt % to 25 wt %, or from 9 wt % to 20 wt % of acrylic acid comonomer or methacrylic acid comonomer. Weight percent is based on the total weight of the EAC. It is understood that the particles of the EAC are distinct from the particles of the acrylic-based polymer present in the acrylic dispersion.

[0063] In an embodiment, the EAC is an ethylene copolymer consisting of (i) ethylene and (ii) from 3 wt % to less than 50 wt % acrylic acid comonomer or methacrylic acid comonomer and the EAC has (i) a number average molecular weight (Mn) from 8.0 kiloDalton (kDa) to 30 kDa, or from 9 kDa to 25 kDa, or from 10 kDa to 20 kDa and (ii) a weight average molecular weight (Mw) from 4.5 kDa to 100 kDa, or from 4.8 kDa to 50 kDa.

[0064] The EAC has a melt index (MI) from 1.0 g/10 min to 100 g/10 min, or from 5 g/10 min to 95 g/10 min, or from 10.0 g/10 min to 95 g/10 min, or from 50 g/10 min to 95 g/10 min.

[0065] The EAC has a density from 0.920 g/cc to 0.960 g/cc, or from 0.930 g/cc to 0.960 g/cc, or from 0.930 g/cc to 0.950 g/cc.

[0066] The EAC has a melting point, Tm, from 70° C. to 110° C., or from 90° C. to 100° C., or from 90° C. to 97° C., or from 90° C. to 95° C.

[0067] The EAC has a Vicat softening point from 48° C. to 95° C., or from 55° C. to 95° C., or from 60° C. to 70° C., or from 60° C. to 65° C.

[0068] The water-based pressure-sensitive adhesive composition has particles of EAC with a volume average particle size from 10 nm, or 25 nm, or 50 nm, or 80 nm, or 100 nm, or 250 nm to 500 nm, or from 750 nm, or from 800 nm, or less than 1100 nm. In an embodiment, the composition has particles of EAC with a volume average particle size from 50 nm to less than 1000 nm, or from 75 to 900 nm, or from 80 nm to 800 nm.

[0069] In an embodiment, the ethylene acid dispersion includes particles of EAC consisting of (i) ethylene and (ii) acrylic acid comonomer, and having one, some, or all of the following properties: [0070] (i) an acrylic acid content from 3 wt % to 20 wt %, or from 11 wt % to 15 wt %; and/or [0071] (ii) an Mn from 7.5 kDa to 20 kDa, or from 9 kDa to 15.5 kDa; and/or [0072] (iii) an Mw from 25.5 kDa to about 150 kDa, or from 45 kDa to about 95 kDa; and/or [0073] (iv) an MI from 1 g/10 min to 100 g/10 min; and/or [0074] (v) a volume average particle size from 50 to 1000 nm, or from 80 nm to 800 nm; and/or [0075] (vi) a density from 0.930 g/cc to 0.950 g/cc, or from 0.935 g/cc to 0.945 g/cc; and/or [0076] (vii) a melting point, Tm, from 80° C. to 110° C., or from 90° C. to 95° C.; and/or [0077] (viii) a Vicat softening point from 55° C. to 95° C., or from 60° C. to 65° C.

[0078] In an embodiment, the ethylene acid dispersion includes particles of EAC consisting of (i) ethylene and (ii) methacrylic acid comonomer, and having one, some, or all of the following properties: [0079] (i) an methacrylic acid content from 3 to 20 wt %, or from 11 to 15 wt %; and/or [0080] (ii) an Mn from 8 kDa to 20 kDa, or from 9 kDa to 15 kDa; and/or [0081] (iii) an Mw from 4.5 kDa to 70 kDa, or from 4.5 kDa to 50 kDa; and/or [0082] (iv) an MI from 1 g/10 min to 100 g/10 min, or from 50 g/10 min to 95 g/10 min; and/or [0083] (v) a volume average particle size from 50 to 1000 nm, or from 80 nm to 800 nm; and/or [0084] (vi) a density from 0.930 g/cc to 0.950 g/cc, or from 0.935 g/cc to 0.945 g/cc; and/or [0085] (vii) a melting point, Tm, from 90° C. to 110° C., or from 90° C. to 95° C.; and/or [0086] (viii) a Vicat softening point from 55° C. to 95° C., or from 60° C. to 65° C.

[0087] Nonlimiting examples of suitable EAC include products sold under the trade names NUCREL™, available from The Dow Chemical Company, and PRIMACOR™, available from SK Global.

[0088] In an embodiment, the water-based pressure-sensitive adhesive composition includes from 0.1 to 25 wt %, or from 0.1 to 10 wt %, or from 0.2 to 6 wt %, or from 0.3 to 4 wt % of the EAC, based on the total dry weight of the water-based pressure-sensitive adhesive composition.

[0089] In an embodiment, the ethylene acid dispersion includes composite particles composed of a first EAC and of a second EAC, wherein the second EAC is different than the first EAC. The second EAC is “different than” the first EAC by way of a different EAC property (comonomer type/content, Mn, Mw, MI, density, Tm, and/or Vicat softening point). The composite particles composed of the first EAC and the second EAC have a volume average particle size from 0.05 micron to 4.0 microns, or from 0.1 microns to 3.5 microns, or from 0.75 micron to 3.0 microns. The ratio of the weight of the first EAC to the second EAC in the composite particles is from 90:10 to 10:90, or from 75:25 to 25:75, or from 60:40 to 40:60, or 50:50 based on the total weight of all composite particles present in the ethylene acid dispersion.

[0090] The ethylene acid dispersion includes a dispersant and/or a neutralizing agent. The dispersant may be present alone, or in combination with, the neutralizing agent. Alternatively, the neutralizing agent may be present alone, or in combination with, the dispersant.

[0091] In an embodiment, the ethylene acid dispersion includes the dispersant. The dispersant provides colloidal stability for the EAC copolymer while in the EAC dispersion. The dispersant is selected from a long chain fatty acid having from 14 to 40 carbon atoms, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polyethylene with acid functionality, a polypropylene with acid functionality, and combinations thereof. In an embodiment, the dispersant is a long chain fatty acid having from 14 to 40 carbon atoms, or from 16 to 36 carbon atoms, or from 18 to 24 carbon atoms and optionally neutralized with a base such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, and/or dimethylethanolamine. Nonlimiting examples of long chain fatty acids suitable for the dispersant include lauric acid (C.sub.12), palmitic acid (C.sub.16), oleic acid (C.sub.18) stearic acid (C.sub.18), arachidic acid (C.sub.20), euricic acid (C.sub.22), behenic acid (C.sub.22), and combinations thereof.

[0092] In an embodiment, the dispersant is an anionic surfactant. Nonlimiting examples of anionic surfactants suitable for the dispersant include sodium lauryl ether sulfonate, sodium dodecylbenzene sulfonate, sodium C.sub.14-C.sub.16 alpha olefin sulfonate, and DOWFAX™ 2A1 available from The Dow Chemical Company.

[0093] In an embodiment, the dispersant is a cationic surfactant. Nonlimiting examples of cationic surfactants suitable for the dispersant include stearamidopropyl dimethylamine.

[0094] In an embodiment, the dispersant is a nonionic surfactant. Nonlimiting examples of nonionic surfactants suitable for the dispersant include poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) and poly(ethylene glycol) alkyl ethers.

[0095] In an embodiment, the dispersant is polyethylene or polypropylene with acid functionality. Nonlimiting examples of polyethylene or polypropylene with acid functionality include ethylene copolymers with acrylic acid, methacrylic acid, maleic acid, or maleic anhydride. In an embodiment, the polyethylene or polypropylene with acid functionality is neutralized with a base such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, and/or dimethylethanolamine.

[0096] In an embodiment, the ethylene acid dispersion includes the neutralizing agent. A “neutralizing agent,” as used herein, is a base which reacts with the acid functionality in the EAC in an acid-base reaction to form a salt. When present, the neutralizing agent is used to control pH and provide stability to the formulated pressure sensitive adhesive composition. The neutralizing agent is present in an amount from greater than 0 wt % to 2 wt %, or from 0.1 wt % to 1.5 wt % based on total dry weight of the water based pressure-sensitive adhesive composition.

[0097] In an embodiment, neutralization of the EAC, is from 25% to 200% on a molar basis; or from 50% to 150% percent on a molar basis, or from 50% to 120% on a molar basis; or or from 50% to 110% percent on a molar basis. Nonlimiting examples of suitable neutralizing agents include hydroxides, carbonates, hydrogen carbonates, amines, and combinations thereof.

[0098] Nonlimiting examples of suitable hydroxides include ammonium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydroxide.

[0099] Nonlimiting examples of suitable carbonates include sodium carbonate, sodium bicarbonate, potassium carbonate, and calcium carbonate.

[0100] Nonlimiting examples of suitable amines include aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, ammonia, monomethylamine, dimethylamine, trimethylamine, 2-amino-2-methyl-1-propanol, triisopropanola mine, diisopropanola mine, N,N-dimethylethanolamine, mono-n-propylamine, dimethyl-n propylamine, N-methanol amine, N-aminoethylethanolamine, N-methyldiethanolamine, monoisopropanolamine, N,N-dimethyl propanolamine, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)-aminomethane, N,N,N′N′-tetrakis(2-hydroxylpropyl)ethylenediamine, 1,2-diaminopropane, 2-amino-2-hydroxymethyl-1,3-propanediol, N,N′-ethylenebis[bis(2-hydroxypropyl)amine]toluene-p-sulphonate, or cyclic amines such as morpholine, piperazine, piperidine, and combinations thereof.

C. Tackifier

[0101] In an embodiment, the water-based pressure sensitive adhesive composition includes a tackifier. Suitable tackifiers include, but are not limited to, rosin resins including rosin acid and/or rosin ester obtained by esterifying rosin acid with alcohols or an epoxy compound and/or its mixture, non-hydrogenated aliphatic C.sub.5 resins, hydrogenated aliphatic C.sub.5 resins, aromatic modified C.sub.5 resins, terpene resins, hydrogenated C.sub.9 resins, (meth)acrylic resins, and combinations thereof. (Meth)acrylic resins suitable as tackifiers are described in references U.S. Pat. No. 4,912,169, US 2002/055587, and U.S. Pat. No. 9,605,188. The water-based pressure-sensitive adhesive composition contains from greater than 0 wt % to 50 wt %, or from 5 wt % to 40 wt %, or from 7 wt % to 30 wt %, or from 8% to 15 wt % of the tackifier based on total dry weight of the water-based pressure sensitive adhesive composition.

D. Additives

[0102] The water-based pressure sensitive adhesive composition may further include one or more optional additives. When the additive is present, nonlimiting examples of suitable additives include thickener, defoamer, wetting agent, mechanical stabilizer, pigment, filler, freeze-thaw agent, neutralizing agent, plasticizer, adhesion promoter, and combinations thereof.

[0103] In an embodiment, the water-based pressure sensitive adhesive composition includes from greater than 0 wt % to 5 wt % thickener, based on the total dry weight of the water-based pressure sensitive adhesive composition. Suitable thickeners include, but are not limited to, ACRYSOL™, UCAR™ and CELLOSIZE™ which are commercially available from The Dow Chemical Company, Midland, Michigan.

[0104] In an embodiment, the water-based pressure-sensitive adhesive composition includes from greater than 0 wt % to 2 wt % of a neutralizing agent, based on the total dry weight of the water-based pressure-sensitive adhesive composition. The neutralizing agent is used to control pH and provide stability to the formulated pressure sensitive adhesive composition. Suitable neutralizing agents include, but are not limited to, aqueous ammonia, aqueous amines, and other aqueous inorganic salts.

E. PSA Composition

[0105] The water-based PSA composition contains [0106] (A) from 40 wt % to 99.9 wt %, or from 93 wt % to 99.8 wt %, or from 95 wt % to 99.7 wt % of the acrylic-based dispersion; [0107] (B) from 10 wt % to 0.1 wt %, or from 7 wt % to 0.2 wt %, or from 5 wt % to 0.3 wt % of the ethylene-based polymer dispersion; and [0108] (C) 0 wt %, or from greater than 0 wt % to 50 wt %, or from 5 wt % to 40 wt %, or from 7 wt % to 30 wt %, or from 8% to 15 wt % tackifier, wherein weight percent is based on the total dry weight of the water-based pressure-sensitive adhesive composition. It is understood that the aggregate dry weight of components (A), (B), and (C) amount to 100 dry wt %.

F. Article

[0109] The present disclosure provides an article. The article includes a first substrate and a layer of a water-based PSA composition on the first substrate (hereafter PSA layer). The water-based PSA composition is any water-based PSA composition as previously disclosed herein and includes the acrylic dispersion (A) composed of particles of (i) the acrylic-based polymer with a glass transition temperature (Tg) less than −20° C., and (ii) the surfactant; the ethylene acid dispersion (B) composed of (i) particles of an ethylene acid copolymer and (ii) a dispersant or a neutralizing agent and (C) optional tackifier. The ethylene acid copolymer contains from 3 wt % to 50 wt %, or from 10 wt % to 20 wt %, or from 11 wt % to 15 wt % of the acid comonomer and has a melt index from 1 g/10 min to 100 g/10 min.

[0110] In an embodiment, the article is a pressure sensitive adhesive article. A “pressure sensitive adhesive article,” as used herein, is an article in which a pressure sensitive adhesive (PSA) is adhered to a first substrate, the PSA having an “available surface,” the available surface being an exposed surface, available to make contact with a second substrate. The “available surface” is composed of any water-based PSA composition as previously disclosed herein. The available surface of the PSA may or may not be in contact with a release material. A “release material,” as used herein, is a material that forms a weak bond with the PSA, such that the PSA may be readily removed by hand to expose the available surface.

[0111] The article includes a first substrate. The first substrate is a film, a cellulose-based material, a fabric, a tape, or a release liner, and combinations thereof.

[0112] In an embodiment, the first substrate is a film. Nonlimiting examples of films suitable for the first substrate include plastic films (unstretched film, or uniaxially stretched film, or biaxially stretched film) such as propylene-based polymer film, ethylene-based polymer film, ethylene/propylene copolymer films, polyester films, poly(vinyl chloride) films, metallized films, foam substrates such as polyurethane foams, and polyethylene foams; and metal foils such as aluminum foils or copper foils.

[0113] In an embodiment, the first substrate is a cellulose-based material. Nonlimiting examples of cellulose-based material suitable for the substrate include paper such as craft paper, crepe paper and Japanese paper, labels, and cardboard.

[0114] In an embodiment, the first substrate is a fabric. Nonlimiting examples of fabric suitable for the substrate included cotton fabrics, staple-fiber fabrics, nonwoven fabrics such as polyester nonwoven fabrics, vinyl on nonwoven fabrics, and combinations thereof.

[0115] In an embodiment, the first substrate is a release liner. Nonlimiting examples of suitable materials for the release liner include fluorocarbon polymers (e.g., polytetrafluoroethylene, polychlorotrifluoro-ethylene, polyvinyl fluoride, polyvinylidene fluoride, a tetrafluoroetylene-hexafluoropropylene copolymer, a chlorofluoroethylene-vinylidene fluoride copolymer, etc.), siliconized paper or film, and non-polar polymers (e.g., olefin-based resins such as ethylene-based polymers and propylene-based polymers.

[0116] In an embodiment, the thickness of the first substrate (film, cellulose-based material, fabric, tape, or release liner) is from 10 microns to 10000 microns, or from 10 microns to 1000 microns, or from 20 microns to 500 microns, or from 50 microns to 100 microns, or from 100 microns to 200 microns, or from 200 microns to 500 microns.

[0117] The PSA layer is formed by applying, on one, or both, first substrate surface(s), the water-based PSA composition, followed by drying or curing. The water-based PSA composition can be any water-based PSA composition as previously disclosed herein. For the application of the PSA composition a coater, e.g., a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, curtain coater, slot die coater, comma coater, knife coater or the like, can be employed. In an embodiment, the surface(s) of the substrate to which the pressure-sensitive adhesive layer is applied is/are subjected to a surface treatment. Nonlimiting examples of suitable surface treatments include a primer coating, and a corona discharge treatment prior to application of the PSA layer onto the substrate surface(s).

[0118] In an embodiment, the thickness of the PSA layer on the substrate surface is from 1 micron to 500 microns, or from 10 microns to 110 microns, or from 30 microns to 90 microns, or from 1 micron to 10 microns, or from 10 microns to 50 microns.

[0119] In an embodiment, the article is a multi-layer PSA article. A “multi-layer PSA article,” as used herein, includes a substrate and two or more PSA layers such that a first PSA layer is in contact with the substrate and a second PSA layer is in contact with the first PSA layer. The multi-layer PSA article may include additional PSA layers wherein each additional PSA layer is in contact with a preceding PSA layer, the PSA layers arranged in a stacked manner. For example, the multi-layer PSA article can include a third PSA layer, the third PSA layer in contact with, and stacked upon, the second PSA layer. The multi-layer PSA article can include a fourth PSA layer, the fourth PSA layer in contact with, and stacked upon, the third PSA layer. The multi-layer PSA article can include a fifth PSA layer, the fifth PSA layer in contact with, and stacked upon, the fourth PSA layer. At least one of the PSA layers of the multi-layer PSA article is composed of any water-based PSA composition as previously disclosed herein.

[0120] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following Examples.

EXAMPLES

[0121] Materials used in the examples are provided in Table 1A and 1B below.

TABLE-US-00001 TABLE 1A Materials used in the comparative samples (CS) and inventive examples (IE) Material/Description Properties Source COHESA 3050 Acrylic dispersion Honeywell An oil-in-water International, Inc. dispersion of an ethylene acrylic acid copolymer (“EAA”) having active solids of 38.5-41.4%, and a viscosity of less than or equal to about 100 cps (Brookfield viscosity at 25° C.) TERGITOL ™ 15-S-9 Nonionic The Dow Chemical surfactant Company AEROSOL OT-75 Anionic surfactant Cytec Solvay Group DISPONIL FES 77 Anionic surfactant BASF SE SURFYNOL 440 Nonionic dynamic Evonik wetting agent ACRYSOL ™ Rheology modifier/ The Dow Chemical RM-2020 thickener Company Sodium carbonate, Various chemicals Sinoreagent ammonium persfulate, Company tert-butyl hydroperoxide, sodium formaldehyde bisulfite, n-dodecyl mercaptan 2-ethylhexyl acrylate Acrylic dispersion The Dow Chemical (“2-EHA”), ethyl monomers Company acrylate (“EA”), methyl methacrylate (“MMA”), acrylic acid (“AA”), butyl acrylate (“BA”) Oleic acid Dispersant Sigma-Aldrich C.sub.18H.sub.34O.sub.2, 282.5 g/mol d = 0.89 g/cc 90% purity reagent grade PRIMACOR ™ 5980i Dispersant SK Global Chemical Melt index 300 PRIMACOR ™ 1410 EAA resin SK Global Chemical PRIMACOR ™ 3440 EAA resin SK Global Chemical

TABLE-US-00002 TABLE 1B EMAA and EAA resins. Density DSC Melt Point, Vicat Softening (g/cm.sup.3) (Tm) (° C.) Point (Vsp) (° C.) MI % MAA* % AA† NUCREL ™ 960 0.94 91 62 60 15 0 NUCREL ™ 699 0.94 94 65 95 11 0 NUCREL ™ 903 0.93 101  81 2.5 9 0 NUCREL ™ 925 0.94 92 67 25 15 0 NUCREL ™ 2806 0.944  83.sup.‡ 48 60 0 18 PRIMACOR ™ 1410 0.938   97.8 81.1 1.5 0 9.7 PRIMACOR ™ 3440 0.938 98 76 10 0 9.7 *Weight percent methacrylic acid comonomer based on total weight EMAA resin †Weight percent acrylic acid comonomer based on total weight EAA resin .sup.‡Data obtained from US 20160145806A1.

TABLE-US-00003 TABLE 1C Dispersions of EMAA and EAA resins Weight % of each Particle Size EMAA or EAA EAC for blends (nm) EMAA 1 NUCREL ™ 960 — 80 EMAA 2 NUCREL ™ 699/ 75/25 100 NUCREL ™ 960 EMAA 3 NUCREL ™ 699/ 75/25 800 NUCREL ™ 960 EMAA 4 NUCREL ™ 903 — 570 EMAA 5 NUCREL ™ 925 — 493 EMAA 6 NUCREL ™ 925/ 75/25 543 NUCREL ™ 960 EAA 1 PRIMACOR ™ 1410 — 223 EAA 2 NUCREL ™ 2806 — 500 EAA 3 PRIMACOR ™ 3440 — 1.080

A. Melt Index (MI)-Melt Viscosity (Mv) Relationship

[0122] Melt Index at 190° C. may be estimated from Melt Viscosity at 140° C. according to the following calculation taken from Shenoy, A. V.; Saini, D. R.; Nadkarni, V. M. Polymer 1983, 24, 722-728. MI at a given temperature, e.g., 140° C., may be estimated from Melt Viscosity at the same temperature as follows:

[00001]$\mathrm{MI}=\frac{49\text{,8}00\times \rho \times L}{\mathrm{Melt}\mathrm{Viscosity}}$

where MI is given in g/10 min, ρ is the polymer density in g/cm.sup.3, L is the weight used in the MI measurement in kg (typically 2.16 kg), and the melt viscosity is given in poise. Next, a rearrangement of the form of the Williams-Landel-Ferry equation provided by Shenoy et al. in the above reference may be used to estimate the MI at one temperature, MI(T.sub.2) e.g., 190° C., from the MI at another temperature, MI(T.sub.1) e.g. 140° C.:

[00002]$\mathrm{MI}\left(T_2\right)=\mathrm{MI}\left(T_1\right)\times 10^{\left(\frac{8.86\left(T_2-T_s\right)}{101.6+\left(T_2-T_s\right)}-\frac{8.86\left(T_1-T_s\right)}{101.6+\left(T_1-T_s\right)}\right)}$

where T.sub.s is the standard reference temperature which is the polymer glass transition temperature plus 50 K, T.sub.2 is the temperature in K at which MI is to be calculated, and T.sub.1 is the temperature in K at which the MI is known. If the polymer glass transition temperature is not known, it may be estimated using the Fox equation from the glass transition temperature of the homopolymers of the component monomers:

[00003]$\frac{1}{T_g}=.Math.\frac{w_i}{T_{g.i}}$

where T.sub.g is the estimated T.sub.g of the desired copolymer, w.sub.i is the weight fraction of the i-th component monomer in the desired copolymer, and T.sub.g,i is the glass transition temperature of the homopolymer of the i-th component monomer.

[0123] As an example, the MI at 190° C. for the EAA Honeywell A-C 5120 polymer may be estimated from its melt viscosity at 140° C. (6 poise), density (0.93 g/cm.sup.3), and glass transition temperature calculated for a copolymer of 85% ethylene and 15% acrylic acid.

TABLE-US-00004 TABLE 1D MI-Mv relationship for various dispersion components Melt Viscosity T.sub.g (K, MI 190° C. Type Name E VA AA 140° C. MI 140° C. ρ calculated) (calculated) EAA Honeywell A-C 5120 85% 15% 6 16673 0.93 208 62309 Oxidized Honeywell A-C 645P* 94% .sup. 6% 3.75 26964 0.94 201 92657 EVA Oxidized Honeywell A-C 655 100%  2.1 47637 0.93 193 156040 PE Oxidized Honeywell A-C 656 100%  1.85 53493 0.92 193 175222 PE EVA Honeywell A-C 405 91.5%.sup.  8.5% 6 16494 0.92 211 63329 EAA Honeywell A-C 540 95%  5% 5.75 17398 0.93 198 59286 EAA Honeywell A-C 580 90% 10% 6.5 15473 0.935 203 55084 EAA Honeywell A-C 5180 80% 20% 6.25 16092 0.935 214 63491 EAA PRIMACOR 5990 80% 20.5%.sup.  n/a n/a 0.955 n/a 1300 EAA PRIMACOR 5980 80% 20.5%.sup.  n/a n/a 0.96 n/a 300 *Monomer composition estimated, wt % based on total weight of material E-ethylene, VA-vinyl acetate, AA-acrylic acid

1. Preparation of Acrylic Dispersion

A. Acrylic Dispersion 1

[0124] Acrylic dispersion 1 is prepared according to the following procedure. A four liter, five-neck reactor equipped with a condenser, a mechanical stirrer, a temperature-controlled thermocouple and inlets for initiators and monomers, is fed with 540 g of deionized (“DI”) water and heated to 87° C. under a gentle nitrogen flow. In a separate container, a monomer emulsion is prepared by mixing 400 g of DI water, 11.9 g of DISPONIL FES 77, 5 g of TERGITOL™ 15-S-9, 4 g of sodium carbonate, and 2,024 g of a monomer mixture composed of 71.5 wt % of 2-ethylhexyl acrylate (“2-EHA”), 18.5 wt % of ethyl acrylate (“EA”), 9 wt % of methyl methacrylate (“MMA”), and 1 wt % of acrylic acid (“AA”). Next, a solution of a mixture of 1.3 g of sodium carbonate and 8.3 g of ammonium persulfate (“APS” as initiator) in 32 g DI water is added into the reactor. Immediately after addition of the solution of sodium carbonate and APS, the monomer emulsion is fed into the reactor. The feeding proceeds for 80 minutes. Upon completion of the monomer emulsion addition, the reaction mixture is cooled to 60° C. before gradual addition of a solution of tert-butyl hydroperoxide (70%) (“t-BHP”) (4.7 g in 23 g DI water) and 2.8 g of sodium formaldehyde bisulfite in 28 g DI water, via two separate feeds over 25 minutes. Upon completion of the feeds, the reaction is cooled to room temperature. The obtained acrylic dispersion 1 is then filtered through 325 mesh filter cloth to prepare the composition for subsequent evaluation work. The obtained acrylic dispersion 1 includes an acrylic-based polymer composed of 71.5 wt % 2-EHA/18.5wt % EA/9 wt % MMA/1 wt % AA, and has a glass transition temperature of −41° C. Weight percent is based on the total dry weight of the acrylic-based polymer.

B. Acrylic Dispersion 2

[0125] Acrylic Dispersion 2 is INVISU™ 4100 available from The Dow Chemical Company.

C. Acrylic Dispersion 3

[0126] Acrylic Dispersion 3 is INVISU™ 3000 available from The Dow Chemical Company.

D. Acrylic Dispersion 4

[0127] A flask set up for semi-continuous emulsion polymerization containing 270 g of water at 90° C. was charged first with sodium peroxodisulfate (1.26 g) in 13 g deionized water and second with 21.2 g of a seed consisting of an aqueous dispersion of an acrylic polymer with mean particle diameter 60 nm at 12% solids content. After two minutes, addition of a feed stream containing sodium peroxodisulfate (3.79 g) in 59.8 g deionized water and a monomer emulsion was begun and continued at a constant rate over 120 minutes at 90° C. The monomer emulsion consisted of 1250 g of monomers in proportions by weight according to Table 2, 180 g of a 33% concentration solution of a sulfuric ester sodium salt of lauryl alcohol ethoxylated by 30 moles of ethylene oxide in water, 5.6 g of a 44% strength solution of DOWFAX™ 2A1 in water, 6.7 g of a 75% concentration solution of dioctylsulfosuccinate sodium salt in ethanol/water, and 295 g of deionized water. After half of the weight of the monomer emulsion was added to the reactor, 72 g of a seed consisting of an aqueous dispersion of an acrylic polymer with mean particle diameter 60 nm at 26% solids content was charged to the reactor within one minute. After the monomer emulsion and the feed stream were fully added to the reactor, an additional 35 g of deionized water was added while the reactor temperature was maintained at 90° C. Next, ammonia (17.9 g of 4.4% concentration in water) was added to the reactor. Finally, a solution of 8% tert-butyl hydroperoxide in water (23 g) and a solution of 10% sodium formaldehyde sulfoxylate in water (19.5 g) were added to the reactor at 90° C. at a constant rate over 60 minutes. After the completion of these feed streams, the reactor contents were cooled to room temperature.

E. Acrylic Dispersion 5

[0128] Using a flask equipped with a mechanical stirrer, an initial aqueous charge composed of 0.51 grams tetrasodium pyrophosphate, 640 grams of deionized water, 1.80 grams anhydrous sodium sulfate, and 1.36 grams ascorbic acid is warmed to 87° C. Next, 28.4 grams of 19% concentration sodium persulfate in water is poured into the flask. Over a period of 2.0 hours, an emulsion made up of 14.7 grams of 50% strength aqueous sodium hydroxide solution, 39.4 grams of a 30% concentration solution of a sulfuric ester sodium salt of lauryl alcohol ethoxylated by 12 moles of ethylene oxide in water, 21.2 grams of 25.0% concentration sodium vinyl sulfonate solution in water, 28.8 grams of a 22% strength solution of sodium dodecylbenzene sulfonate in water, 6.6 grams of itaconic acid, 236 grams of water, 321.2 grams of methyl methacrylate, 55.2 grams of styrene, 1,592.4 grams of 2-ethylhexyl acrylate, 679.3 grams of ethyl acrylate, and 14.4 grams of acrylic acid is gradually fed into the flask. At the outset, the rate of addition is 5.0 grams per minute for the first 5.0 minutes. It is then raised steadily to 25.0 grams per minute over the span of 35 minutes. After 75 minutes of total feed time, the rate is raised to 35.0 grams per minute. From the outset of the emulsion feed, 94 grams of a sodium peroxodisulfate solution at 11% strength in water is added at a constant rate over 2.3 hours, and the reactor temperature is kept at 85 to 87° C.

[0129] After the completion of the feeds and at roughly 70° C., a solution of 2.76 grams sodium bisulphite, 1.8 grams acetone and 44.4 grams water, and, at the same time, 47.6 grams of a 5.5% concentration solution of tert-butyl hydroperoxide is dispensed to the flask over a period of 45 minutes. A copolymer dispersion of pressure-sensitive adhesive is produced with 70% solids by weight.

F. Acrylic dispersion 6

[0130] Using a flask equipped with a mechanical stirrer, a charge composed of 1.34 g tetrasodium pyrophosphate, 269 g of deionized water, and 0.68 g ascorbic acid is warmed to 86° C. Next, 28 g of 6.6% concentration sodium persulfate in water is poured into the flask. Over a span of four hours, an emulsion made up of 24.5 g of 10% strength aqueous sodium hydroxide solution, 30 g of a 33% concentration solution of a sulfuric ester sodium salt of lauryl alcohol ethoxylated by 30 moles of ethylene oxide in water, 10.6 g of 25.0% concentration sodium vinylsulfonate solution in water, 5 g of a 44% strength solution of DOWFAX™ 2A1 in water, 2.2 g of lauryl alcohol ethoxylated with 7 mol of ethylene oxide, 172 g of water, 27.6 g of styrene, 1,079.2 g of 2-ethylhexyl acrylate, 55.2 g of vinyl acetate, 162 g of methyl methacrylate, and 7.2 g of acrylic acid is gradually dispensed into the flask. At the outset, the rate of addition is 1.42 g/minute for the first six minutes. The rate of addition is then raised steadily to 7.1 g/minute over the span of forty minutes. From the outset of the emulsion feed, 148 g of a sodium peroxodisulfate solution at 5% strength in water is added at a constant rate over five hours, and the reaction medium is maintained from 85 to 87° C.

[0131] After the completion of the feeds and at roughly 70° C., a solution of 1.38 g sodium bisulphite, 0.9 g acetone and 22.2 g water, and, at the same time, 23.8 g of a 5.5% concentration solution of tert-butyl hydroperoxide is dispensed to the flask during the span of sixty minutes.

G. Acrylic Dispersion 7

[0132] Sodium carbonate (0.01% BOM, 0.55g) was added as buffer to a 96° C. kettle charge of a water (518g) swept with nitrogen, equipped with overhead stirring, thermometer, and reflux condenser. This was followed by ammonium persulfate (0.217% BOM, 5.9g) as initiator and a preform seed charge (100 nm starting particle size, 1.251% BOM, 70.79g) to set the initial particle size. A monomer emulsion feed and cofeed were started. The monomer emulsion consisted of sodium carbonate (0.02% BOM, 1.4g), itaconic acid (0.2%, 5.1g), acrylic acid (0.8% BOM, 20.4g), disodium ethoxylated alcohol half ester of sulfosuccinic acid (0.17%, 14.3g), sodium dodecylbenzenesulfonate (0.21% BOM, 24.2g), butyl acrylate (71.1% BOM, 1818g), methyl methacrylate (6.0% BOM, 152.8g), styrene (1.6% BOM, 40.8g) and water (16.8% of total monomer emulsion, 4 1 lg) and was fed for 75 minutes. The co-feed of ammonium persulfate (0.173% BOM, 4.6g) was fed for 75 minutes. The temperature of the reaction was controlled between 88-90° C. Partway through the monomer emulsion feed an intercept of sodium dodecylbenzenesulfonate (0.235% BOM, 26.5g) was added to the kettle. Once the addition of the monomer emulsion concluded, it was held at temperature. After fifteen minutes the kettle was cooled to 75° C. and dilute iron sulfate (0.001% BOM, 0.03g) and tetrasodium ethylenediaminetetraacetate (0.001% BOM, 0.03g) was added to the kettle. Subsequently a monomer emulsion feed and cofeeds were started. The monomer emulsion consisted of tetrasodium 1,1-diphosphonatoethanol (0.002%, 0.1 g), acetic acid (0.03% BOM, 0.6g), sodium dodecylbenzenesulfonate (0.05% BOM, 5.3g), butyl acrylate (5% BOM, 127. 8g), butyl methacrylate (15% BOM, 353.3g), 3-methylmercaptopropionate (0.38% BOM, 9.8g) and water (105.7g) for 20 minutes. One cofeed consisted of t-butlyhydroperoxide (0.4% BOM, 15.1g) and was fed for 50 minutes. The other cofeed consisted of sodium hydroxymethanesulfonate (0.24% BOM, 8.1g) and was fed for 50 minutes. During the monomer emulsion feed the temperature was controlled at 74-76° C. Once the monomer emulsion finished, the batch was allowed to cool to 65° C. The dispersion was then neutralized with ammonium hydroxide until a pH of 7 was obtained. After neutralization the batch was cooled to below 35° C.

[0133] Table 2 below summarizes the properties for acrylic dispersions 1-7 where component amounts are shown as weight percent based on dry weight of the acrylic dispersion.

TABLE-US-00005 TABLE 2 Acrylic dispersions composition and properties Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic Dispersion Dispersion Dispersion Dispersion Dispersion Dispersion Dispersion Component 1 2 3 4 5 6 7 2-EHA 71.5 80 59.5 80.9 — MA — 8 — — — MMA 9 8 12.0 12.1 6.0 Styrene — 2 2.1 2.1 1.6 2- — 1 — — — hydroxyethyl acrylate AA 1 1 0.55 0.55 0.8 BA — 0 — — 76.1 EA 18.5 0 25.4 — Itaconic acid — — 0.2 — 0.2 Sodium vinyl — — 0.25 0.25 — sulfonate VA — — — 4.1 — n-butyl — — — — 15 methacrylate Property pH 7.5 7.75 4.75 6.1 4.5 4.2 7.0 Solids (%) 66.4 62 68 61 70 66 64 Viscosity (cP) — 1000 — — — — — Tg −41° C. −45° C. −53° C. −40° C. −33° C. −46 −26° C. Wt % based on dry weight of acrylic dispersion

2. Preparation of Ethylene Acid Dispersion

[0134] An aqueous ethylene acid dispersion was prepared utilizing a Bersdorf ZE25 48 LID 25 mm twin screw extruder (Kraus-Maffei Corporation, Florence KY, USA) rotating at 450 rpm according to the following procedure. The EAC resin was supplied to the feed throat of the extruder via a Schenck Mechatron loss-in-weight feeder and K-tron loss in weight feeders to control blend composition. The EAC resin was melt blended, and then emulsified in the presence of initial aqueous stream (IA) and neutralized with a neutralizing agent (potassium hydroxide (KOH), ammonia, or dimethylethanolamine) both injected using ISCO dual syringe pumps (from Teledyne Isco, Inc., Lincoln NE, USA). The dispersion phase was then conveyed forward to the dilution and cooling zone of the extruder where additional dilution water was added by ISCO dual syringe pumps to form the aqueous dispersion having solid level content less than 70 weight percent. The barrel temperature of the extruder was set to 140-150 ° C. After the ethylene acid dispersion exited the extruder, it was further cooled and filtered via a 200 μm mesh size bag filter.

[0135] Specific feed rates and results are shown in Table 3 below.

TABLE-US-00006 TABLE 3 Preparation parameters for ethylene acid dispersions Dilution EMAA/EAA EMAA/EAA Dispersant, IA, Neutralizing Base, Water, Sample Feed 1, g/min Feed 2, g/min g/min mL/min mL/min mL/min EMAA 1 NUCREL ™ 960, — — 41.0 Dimethylethanolamine, 217 40.0 7.0 EMAA 2 NUCREL ™ 699, NUCREL ™ 960, — 37.5 30% potassium 200 56.8 18.9 hydroxide, 6.3 EMAA 3 NUCREL ™ 699, NUCREL ™ 960, — 38.0 30% potassium 125 56.8 18.9 — hydroxide, 4.6 EMAA 4 NUCREL ™ 903, — PRIMACOR ™ 32 Dimethylethanolamine, 110 52.9 5980i, 22.7 17.8 EMAA 5 NUCREL ™ 925, — — 33.1 30% potassium 275 75.7 hydroxide, 5.8 EMAA 6 NUCREL ™ 925, NUCREL ™ 960, — 33.9 30% potassium 275 56.8 18.9 hydroxide, 4.9 EAA 1 PRIMACOR ™ — PRIMACOR ™ 33.4 Dimethylethanolamine, 120 1410, 47.6 5980i, 20.4 11.2 EAA 2 NUCREL ™ 2806, — — 19.2 28 wt % Ammonia, 3.4 105 50.0 EAA 3 PRIMACOR ™ — PRIMACOR ™ 30.5 Dimethylethanolamine, 130 3440, 53.0 5980i, 22.7 13.0

3. Preparation of Pressure Sensitive Adhesive Composition

[0136] Water-based pressure sensitive adhesive composition was formulated as follows. All samples were formulated with a wetting agent, 0.3% (wet/wet) SURFYNOL 440 wetting agent obtained from Evonik (“440”), based on total dispersion, to improve wet-out for lab drawdowns unless otherwise specified. The viscosity was then adjusted to approximately 600 mPa*s (600 cps) (Brookfield, RVDV, 30 rpm, 63#) using a thickener, ACRYSOL™ DR-5500, available from The Dow Chemical Company, Midland, Michigan (“DR-5500”), and final pH was adjusted to 7.0 to 7.5 using ammonium hydroxide.

[0137] The acrylic dispersion was blended with ethylene acid dispersion according to the dosage level shown in the respective table (wet or dry weight based on total weight of acrylic dispersion) under proper agitation.

4. Preparation of PSA Article

Lab Drawdowns:

[0138] Polypropylene (“PP”) film (60 microns in thickness) was pre-treated by corona treatment before lamination. Samples of the water-based PSA composition were coated onto a release paper and dried at 80° C. for 5 minutes. The PP film was laminated with the water-based pressure-sensitive adhesive coated release liner (“adhesive laminate”).

[0139] Performance testing was conducted after the adhesive laminate was conditioned in a controlled environment (22.2 to 23.3° C. (72 to 74° F.), 50% relative humidity) for at least 1 day (24 hours).

[0140] High density polyethylene (HDPE) panels purchased from Cheminstruments (510 Commercial Dr., West Chester Township, OH 45014) are cleaned and conditioned prior to being used for adhesive testing. Panels are wiped with lint-free, non-abrasive cloth soaked in isopropanol to remove any adhesive residue from prior testing. Care is taken not to scratch the surface. Once panel surface appears clean, an additional wipe is performed using isopropanol. The HDPE panel is conditioned for a minimum of 4 hours but no more than 24 hours at 22.2 to 23.3° C. (72 to 74° F.), 50% relative humidity.

5. PSA Application Tests

[0141] Performance testing was conducted after the water-based PSA composition in the adhesive laminate was completely dried and conditioned in a controlled environment (22.2 to 23.3° C., 50% relative humidity) testing laboratory for at least overnight, and in some instances after as many as 120 hours under 12 kg of weight.

[0142] The composition of the dried PSA's are provided in Table 4. The peel adhesion, loop tack, and shear data for adhesive laminates with the dried PSA are provided in Tables 5 and 6.

6. Performance Testing of Formulations with EMAA1

[0143] EMAA1 was formulated with Acrylic Dispersion 2 and PSA application tests were performed according to the methods described above.

TABLE-US-00007 TABLE 4 Description of comparative samples and inventive examples Parts of Acrylic Parts of Additive Dispersion 1 Acrylic Additive (wt % by wet Dispersion 2 (Parts by based on weight by weight dry weight) dry weight) CS1 100 Cohesa 3050 (0.4) 0.6 CS2 100 0 0 IE1 100 EMAA1 (0.4) 0.6 IE2 100 EMAA1 (2) 2.9 CS—comparative sample, IE—inventive example

TABLE-US-00008 TABLE 5 Peel, loop tack, and shear data of dried adhesive laminates CS1 CS2 IE1 IE2 90° Peel (HDPE), 20 N/2.54 cm 2.9 2.6 3.1 2.6 min 90° Peel (HDPE), 24 N/2.54 cm 3.6 3.4 4.1 3.9 hr 90° Peel (SS), 20 min N/2.54 cm 7.7 7.5 7.9 7.4 90° Peel (SS), 24 hr N/2.54 cm 11.6 14.7  15.9  14.5  90° Peel (Glass), 20 N/2.54 cm 5.8 5.8 5.8 5.4 min 90° Peel (Glass), 24 N/2.54 cm 7.1 7.5 7.5 7.6 hr Loop Tack (HDPE) N/6.45 cm.sup.2 5.1 5.4 4.7 4.9 Loop Tack (SS) N/6.45 cm.sup.2 8.7 8.3 7.5 6.9 Loop Tack (Glass) N/6.45 cm.sup.2 9.6 9.0 8.9 8.5 Shear (SS), 1″ × 1″, hrs 75 200+   200+   175    1 kg Shear (Glass), 1″ × 1″, hrs 60 200+   200+   200+   1 kg

[0144] The 90° HDPE peel adhesion (24 hr) observed for PSA articles (laminates) prepared from formulations of acrylic dispersion 1 with EMAA copolymer dispersions with low MI is unexpectedly higher than that of the sample with Cohesa 3050 (CS1) and the sample without any additive (CS2).

[0145] The formulation with low molecular weight and higher MI (Cohesa 3050 ethylene acrylic acid dispersion (CS1)) has lower adhesion to HDPE (lower 90° HDPE peel adhesion, 3.6 N/2.54 cm) than each inventive example IE1 (4.1 N/2.54 cm) and IE2 (3.9 N/2.54 cm). This is surprising because typically lower molecular weight additives such as high MI EAA copolymer dispersions are advantaged for increasing HDPE adhesion.

7. Performance Testing of Formulations with EMAA2 and EMAA3

[0146] In a separate experiment, EMAA2 and EMAA3 were formulated with Acrylic Dispersion 2 and PSA application tests were performed according to the methods described above.

TABLE-US-00009 TABLE 6 Description of comparative samples and inventive examples Parts of Acrylic Additive Additive (wt % Dispersion 2 (Parts by based on total by wet weight dry weight) dry weight) CS2 100 0 0 IE3 100 EMAA2 (4) 6.1 IE4 100 EMAA3 (0.4) 0.6 CS—comparative sample, IE—inventive example

TABLE-US-00010 TABLE 7 Peel, loop tack, and shear data of dried adhesive laminates Parts of Acrylic 90° Peel 90° Peel Loop Disper- Additive (HDPE), (HDPE), Tack sion 2 (Parts by 20 min, 24 h, (HDPE), by weight Dry Weight) N/2.54 cm N/2.54 cm N CS2 100 0 4.7 5.1 5.0 IE3 100 EMAA2 (4) 5.2 5.1 4.9 IE4 100 EMAA3 (0.4) 4.3 4.7 5.5

[0147] Each inventive example has higher adhesion to HDPE than CS2 in some respects. IE3 has higher 90° HDPE peel adhesion at 20 minutes than CS2, 5.2 N/2.54 cm vs. 4.7 N/2.54 cm. IE4 has higher HDPE tack than CS2, 5.5 N vs. 5.0 N. This is surprising because high molecular weight and low MI EMAA copolymer dispersions are not expected to increase HDPE adhesion. 8. Performance testing of formulations with EMAA1 with other acrylic dispersions

[0148] The acrylic dispersion was blended with the EMAA dispersion according to the dosage level shown in the respective table (wet weight based on total weight of acrylic dispersion) under proper agitation to achieve mixing.

TABLE-US-00011 TABLE 8 EMAA1 parts by Acrylic dispersion (parts by weight) weight IE7 Acrylic dispersion 3 (100) 1 IE8 Acrylic dispersion 3 (100) 1 IE9 Acrylic dispersion 4 (100) 1 IE10 Acrylic dispersion 5 (100) 1 IE11 Acrylic dispersion 6 (100) 1 IE12 Acrylic dispersion 7 (100) 1

[0149] 9. Performance Testing of Formulations with EMAA 4, EMAA 5, EMAA 6, EAA 1, and EAA 2

[0150] In a separate experiment, EMAA 4, EMAA 5, EMAA 6, EAA 1, and EAA 2 were formulated with Acrylic Dispersion 2 and PSA application tests were performed according to the methods described above.

TABLE-US-00012 TABLE 9 Description of comparative samples and inventive examples Parts of Acrylic Additive Additive (wt % Dispersion 2 (Parts by based on total by wet weight dry weight) dry weight) CS2 100 0 0 IE13 100 EAA 1 (0.4) 0.6 IE14 100 EAA 1 (2) 3 IE15 100 EMAA 4 (0.4) 0.6 IE16 100 EMAA 4 (2) 3 IE17 100 EMAA 5 (0.4) 0.6 IE18 100 EMAA 6 (0.4) 0.6 IE19 100 EAA 2 (0.4) 0.6 IE20 100 EAA 2 (2) 3 CS—comparative sample, IE—inventive example

TABLE-US-00013 TABLE 10 Peel, loop tack, and shear data of dried adhesive laminates Parts of 90° Peel 90° Peel Acrylic Additive (HDPE), (HDPE), Dispersion 2 (Parts by 20 min, 24 h, by weight Dry Weight) N/2.54 cm N/2.54 cm CS2 100 0 2.8 3.8 IE13 100 EAA 1 (0.4) 2.9 4.7 IE14 100 EAA 1 (2) 3.0 4.3 IE16 100 EMAA 4 (2) 3.2 4.6 IE17 100 EMAA 5 (0.4) 2.7 4.0 IE18 100 EMAA 6 (0.4) 2.8 4.4 IE19 100 EAA 2 (0.4) 3.7 4.2 IE20 100 EAA 2 (2) 4.4 4.3

[0151] Each inventive example has higher adhesion to HDPE than CS2 at either 20 minutes dwell time or at 24 hours dwell time. IE13-16 and IE19-20 have higher 90° HDPE peel adhesion at 20 minutes than CS2. While 1E17 and 1E18 do not exceed the 90° HDPE peel adhesion at 20 minutes of CS2, with a longer dwell time they surpass the CS2 with higher 90° HDPE peel adhesion at 24 hours. This is surprising because high molecular weight and low MI EMAA or EAA copolymer dispersions are not expected to increase HDPE adhesion. Performance testing of formulations with EAA 3

[0152] In a separate experiment, EAA 3 was formulated with Acrylic Dispersion 2 and PSA application tests were performed according to the methods described above.

TABLE-US-00014 TABLE 11 Description of comparative samples and inventive examples Parts of Acrylic Additive Additive (wt % Dispersion 2 (Parts by based on total by wet weight dry weight) dry weight) CS2 100 0 0 IE21 100 EAA 3 (0.4) 0.6 IE22 100 EAA 3 (2) 3 CS—comparative sample, IE—inventive example

TABLE-US-00015 TABLE 12 Peel, loop tack, and shear data of dried adhesive laminates Parts of 90° Peel 90° Peel Acrylic Additive (HDPE), (HDPE), Dispersion 2 (Parts by 20 min, 24 h, by weight Dry Weight) N/2.54 cm N/2.54 cm CS2 100 0 3.6 5.1 IE21 100 EAA 3 (0.4) 3.9 5.9 IE22 100 EAA 3 (2) 4.9 6.2

[0153] Inventive examples IE21 and IE22 have higher adhesion to HDPE than CS2 as measured by 90° HDPE peel adhesion at 20 minutes and at 24 hours at two different loading levels. This is surprising because high molecular weight and low MI EAA copolymer dispersions are not expected to increase HDPE adhesion.

[0154] It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.