Adhesive composition

Abstract

The present disclosure provides an adhesive composition comprising (A) multi-stage latex polymer particles, (B) a linear diamine base, and (C) an ethoxylated surfactant. The (A) multi-stage latex polymer particles comprise (i) a first stage polymer comprising an acrylic acid monomer and a first vinyl monomer, and (ii) a second stage polymer comprising a methacrylic acid monomer and a second vinyl monomer, with the proviso that the second vinyl monomer is different from the methacrylic acid monomer. The first stage polymer is bonded to the second stage polymer.

Description

Background Art

[0001] In the adhesive industry, acrylic polymers are used in the production of pressure-sensitive adhesives (PSAs) with adhesive properties suitable for labels and other applications. Continuous efforts are being made to develop polymers that exhibit improved long-term adhesive performance, such as shear.

[0002] The art recognizes the need for adhesive compositions containing acrylic polymers suitable for use as pressure-sensitive adhesives. The art further recognizes the need for adhesive compositions that exhibit sufficient long-term adhesive performance in PSA applications.

Summary of the Invention

[0003] The present disclosure provides an adhesive composition. The adhesive composition contains (A) multi-stage latex polymer particles, (B) a linear diamine base, and (C) an ethoxylated surfactant. The (A) multi-stage latex polymer particles include (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer. The first-stage polymer is bonded to the second-stage polymer.

[0004] The present disclosure also provides an article. The article includes a substrate and a coating on the substrate. The coating contains an adhesive composition. The adhesive composition contains (A) multi-stage latex polymer particles, (B) a linear diamine base, and (C) an ethoxylated surfactant. The (A) multi-stage latex polymer particles include (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer. The first-stage polymer is bonded to the second-stage polymer.

[0005] Definition Any reference to the Periodic Table of the Elements is as published by CRC Press, Inc., 1990 - 1991. References to the groups of elements in this table are by a new notation for numbering the groups.

[0006] For purposes of U.S. patent practice, the contents of any patent, patent application, or publication that is referenced are incorporated by reference in their entirety (or an equivalent U.S. version is so incorporated by reference) with respect to definitions of disclosure (especially to the extent not inconsistent with any definitions provided in this disclosure) and general knowledge in the art.

[0007] The numerical ranges disclosed herein include all values from the lower value to the upper value. In the case of ranges that include explicit values (e.g., ranges from 1, or 2, or 3 - 5, or 6, or 7), any sub - range between any two of the explicit values is also included (e.g., the above range 1 - 7 includes sub - ranges 1 - 2, 2 - 6, 5 - 7, 3 - 7, 5 - 6, etc.).

[0008] Unless otherwise indicated, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure, implicit from the context or not a convention in the art.

[0009] An "adhesive composition" is a mixture of components that can join a substrate of interest under heat and / or pressure. Non - limiting examples of suitable adhesive compositions include pressure - sensitive adhesive (PSA) compositions and hot - melt adhesive (HMA) compositions. A "pressure - sensitive adhesive (PSA) composition" is a mixture of components that can join a substrate of interest under pressure without the need for heat. A "hot - melt adhesive (HMA) composition" is a mixture of components that can join a substrate of interest under heat, or more typically, under heat and pressure.

[0010] "Alkyl" and "alkyl group" refer to saturated linear, cyclic, or branched hydrocarbon groups. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2-methylpropyl), and the like. In one embodiment, the alkyl group has 1 to 20 carbon atoms.

[0011] "Alkenyl" or "alkenyl group" refers to a hydrocarbyl group containing at least one C=C double bond. The alkenyl group can be linear, cyclic, or branched. Non-limiting examples of suitable alkenyl groups include ethenyl group, n-propenyl group, i-propenyl group, n-butenyl group, t-butenyl group, i-butenyl group, and the like.

[0012] "Aralkyl" and "aralkyl group" refer to organic radicals obtained from aromatic hydrocarbons by replacing one or more hydrogen atoms with aryl groups.

[0013] "Aryl" and "aryl group" refer to organic radicals obtained from aromatic hydrocarbons by deleting one hydrogen atom therefrom. The aryl group can be a monocyclic system and / or a fused ring system, and each of these rings preferably contains 5 to 7, or 5 to 6 atoms. Structures in which two or more aryl groups are combined via single bond(s) are also included. Specific examples include, but are not limited to, phenyl, tolyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, benzofluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

[0014] Terms such as "blend" and "polymer blend" refer to a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase-separated. Such blends may or may not contain one or more domain structures as determined from transmission electron spectroscopy, light scattering, X-ray scattering, and any other method used to measure and / or identify domain structure.

[0015] The term "composition" refers to a mixture of the materials that make up the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0016] The terms "comprising", "including", "having", and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not they are specifically disclosed. To avoid any doubt, all compositions recited in claims through use of the term "comprising" may contain any additional additives, auxiliaries, or compounds, whether polymerized or not, unless the contrary is stated. In contrast, the term "consisting essentially of" excludes any other component, step, or procedure from the scope of any subsequent recitation, except for those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically described or listed. The term "or" refers to the listed items individually and in any combination, unless otherwise stated. The use of the singular includes the use of the plural and vice versa.

[0017] "Crosslinkability" and "curability" mean that the polymer, before or after being formed into an article, has not been cured or crosslinked and has not been exposed to a process that induces significant crosslinking, although the polymer includes additives or functionality that will result in significant crosslinking when subjected to or exposed to such a process (e.g., exposure to water or drying).

[0018] "Crosslinked" and similar terms mean that the polymer composition has, before or after being formed into an article, no more than 90 weight percent xylene or decalin extractable (i.e., a gel content of at least 10 weight percent).

[0019] "Diene" means an unsaturated hydrocarbon containing two double bonds between carbon atoms. The diene can be a conjugated, non-conjugated, straight-chain, branched-chain or cyclic hydrocarbon diene having 6 to 15 carbon atoms. Non-limiting examples of suitable dienes include 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene.

[0020] "Fabric" means a woven structure or non-woven (knitted, etc.) structure formed from individual fibers or yarns.

[0021] "Fiber" and similar terms refer to an elongated column of intertwined filaments. The fiber diameter can be measured and reported in various ways. Generally, the fiber diameter is measured in denier per filament. Denier is a textile term defined as the number of grams of the fiber per 9,000 meters of its length. Monofilament generally refers to an extruded strand having more than 15, usually more than 30, denier per filament. Microdenier fiber generally refers to a fiber having no more than 15 denier. Microdenier (also known as microfiber) generally refers to a fiber having a diameter of no more than 100 micrometers.

[0022] The term "filament" and similar terms generally refer to a strand of a single continuous elongating material having a circular cross-section and a length-to-diameter ratio of greater than 10.

[0023] "Halogen" refers to the elements of Group 17 of the IUPAC periodic table, including fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).

[0024] "Heteroatom" refers to an atom other than carbon or hydrogen. Heteroatoms can be non-carbon atoms from Groups IV, V, VI, and VII of the periodic table. Non-limiting examples of heteroatoms include F, N, O, P, B, S, and Si.

[0025] The terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or acyclic species. Non-limiting examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and alkynyl groups.

[0026] "Knit fabric" is formed by intertwining yarns or fibers into a series of interconnected loops by hand, with knitting needles, or on a machine. The fabric can be formed by knitting in the warp or weft direction, plain knitting, and circular knitting. Non-limiting examples of suitable warp knitting include tricot, raschel power net, and lace. Non-limiting examples of suitable weft knitting include circular knitting, plain knitting, and seamless (which is often considered a subset of circular knitting).

[0027] "Latex polymer" refers to a polymer compound prepared by aqueous emulsion polymerization. The latex polymer exists as particles suspended throughout a continuous aqueous medium that is a stable dispersion.

[0028] "Non-woven" refers to a web or fabric having a structure of individual fibers or yarns that are randomly interlaced but not in a distinguishable pattern as in the case of knitted fabrics.

[0029] "Polymer" refers to a polymer compound prepared by polymerizing monomers, whether of the same or different types. Thus, the general term "polymer" encompasses "homopolymers" (used to refer to polymers prepared from only one type of monomer, with the understanding that trace impurities may be incorporated into the polymer structure), and the term "interpolymer", which includes copolymers (used to refer to polymers prepared from two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from four or more different types of monomers. For example, trace impurities such as catalyst residues can be incorporated into and / or within the polymer. This term also encompasses all forms of copolymers, such as random, block, etc. Polymers are often referred to as being "made from", "based on", "containing" one or more specific monomers, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the polymerization residue of that specific monomer, rather than the non-polymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomers.

[0030] "Replacement hydrocarbyl" and "replacement hydrocarbon" refer to a hydrocarbyl group substituted with one or more non-hydrocarbyl substituents. Non-limiting examples of non-hydrocarbyl substituents include heteroatoms, moieties containing heteroatoms, oxygen-containing moieties (e.g., alcohol, acrylate, acrylic acid, aldehyde, carboxylic acid, ester, ether, ketone, and peroxide groups), and nitrogen-containing moieties (e.g., amide, amine, azo, imide, imine, nitrate, nitrile, and nitrite groups).

[0031] "Fabric" is a flexible material composed of a network of natural fibers, artificial fibers, and combinations thereof. Fabrics include fabrics and cloth.

[0032] "Weight of the polymer" refers to the dry weight of the polymer.

[0033] "Woven" refers to a web or fabric having an identifiable pattern of individual fibers or yarn-like structures arranged in an alternating pattern in a regular pattern. Non-limiting examples of woven fabrics include knitted fabrics.

[0034] "Yarn" is a single continuous filament that is twisted or otherwise intertwined and can be used in the manufacture of woven or knitted fabrics.

[0035] Test Methods The flash point refers to the lowest temperature at which a volatile liquid vaporizes and forms an ignitable mixture in air but does not continue to burn (to be compared with the combustion point). The flash point is measured according to ASTM D 3278.

[0036] The glass transition temperature (Tg) is measured according to ASTM-D3418-15.

[0037] The hydrophilic-lipophilic balance (HLB) of a surfactant is a measure of the degree to which the surfactant is hydrophilic or lipophilic. The HLB is determined by calculating values for different regions of its molecule as described by William C. Griffin in “Classification of Surface-Active Agents by HLB,” 1 Journal of the Society of Cosmetic Chemists 5, 311-26 (1949) and “Calculation of HLB Values of Non-Ionic Surfactants,” 5 Journal of the Society of Cosmetic Chemists 4, 249-56 (1954), the contents of which are incorporated herein by reference.

[0038] Loop tack is measured for both stainless steel substrates and high density polyethylene (HDPE) substrates in accordance with ASTM 6195-03, Test Method - A.

[0039] pH is measured in accordance with ASTM E70-07 (2015).

[0040] Shear is measured in accordance with the PSTC 107 method. Results are reported in units of time.

[0041] The viscosities of the linear diamine base and the composition are measured at 25 °C using a Brookfield LV viscometer equipped with a #3 cylindrical spindle at 30 revolutions per minute (RPM).

[0042] The weight average molecular weight (Mw) is measured using a gel permeation chromatography (GPC) system. Mw is calculated according to the following formula (1).

Equation

[0043] The 90° peel is measured according to PSTC 101, Test Method F. The results are reported as grams per inch (g / in).

DETAILED DESCRIPTION OF THE INVENTION

[0044] The present disclosure provides an adhesive composition. The adhesive composition contains (A) multi-stage latex polymer particles, (B) a linear diamine base, and (C) an ethoxylated surfactant. The (A) multi-stage latex polymer particles include (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer. The first-stage polymer is bonded to the second-stage polymer.

[0045] In one embodiment, the adhesive composition is a pressure-sensitive adhesive (PSA) composition.

[0046] A. Multi-stage latex polymer particles The adhesive composition contains multi-stage latex polymer particles. The multi-stage latex polymer particles include (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer. The first-stage polymer is bonded to the second-stage polymer.

[0047] "Multi-stage latex polymer particles" ("MSLPP") are latex polymers in which each particle contains a first-stage polymer and a second-stage polymer, and the first-stage polymer is bonded to the second-stage polymer. As used herein with respect to MSLPP, the term "bonded" refers to a first-stage polymer and a second-stage polymer that are covalently bonded or associated with each other in a core-shell structure, where the first-stage polymer forms the core and the second-stage polymer forms the shell. MSLPP is prepared in two or more polymerization stages. In one stage, an emulsion polymerization process is carried out to produce first-stage polymer particles. In a subsequent stage, an emulsion polymerization process is carried out in the presence of the first-stage polymer particles to form the second-stage polymer. In one embodiment, there is a certain period during which no detectable polymerization occurs between the formation of the first-stage polymer and the formation of the second-stage polymer. In the formation of the second-stage polymer, more than half (by weight based on the weight of the second-stage polymer) of the second-stage polymer forms on the surface of the first-stage polymer particles, and the second-stage polymer binds to the first-stage polymer. The second-stage polymer encapsulates or substantially encapsulates the first-stage polymer particles. One or more additional polymerization stages are optionally carried out (i) before the formation of the first-stage polymer, and / or (ii) between the formation of the first-stage polymer and the formation of the second-stage polymer, and / or (iii) after the formation of the second-stage polymer, and / or (iv) combinations thereof.

[0048] i. The first-stage polymer The multi-stage latex polymer particles include a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer.

[0049] The first-stage polymer contains an acrylic acid monomer. The "acrylic acid monomer" (or "AA") is a compound having the following structure (1).

Chemical formula

[0050] The first-stage polymer contains a first vinyl monomer. The "vinyl monomer" is a compound having the following structure (2).

Chemical formula

[0051] Non-limiting examples of suitable vinyl monomers include styrene (STY), α-methylstyrene, ethylene, ethylene ester, diene, vinyl acetate, vinyl neodecanoate, acrylonitrile (AN), (meth)acrylonitrile, meth(acrylic) acid (MAA), acrylic acid, (meth)alkyl acrylate, methacrylamide, acrylamide, butyl acrylate (BA), ethyl acrylate (EA), methyl methacrylate (MMA), allyl methacrylate (ALMA), (meth)hydroxyalkyl acrylate, divinylbenzene (DVB), 2-ethylhexyl acrylate (EHA), and combinations thereof.

[0052] The first vinyl monomer is different from the acrylic acid monomer (AA). In other words, the first vinyl monomer is different from AA in composition and / or structure.

[0053] In one embodiment, the first vinyl monomer is selected from EHA, MMA, and combinations thereof.

[0054] In one embodiment, the first-stage polymer contains, consists essentially of, or consists of (i) AA, and (ii) the first vinyl monomer is selected from EHA, MMA, and combinations thereof.

[0055] In one embodiment, the first-stage polymer contains, consists essentially of, or consists of (i) AA, (ii) EHA, and (iii) MMA.

[0056] In one embodiment, the first-stage polymer has a weight-average molecular weight Mw of 50,000 g / mol, or 84,000 g / mol, or 200,000 g / mol, or 300,000 g / mol, or 340,000 g / mol to 400,000 g / mol, or 500,000 g / mol, or 750,000 g / mol, or 1,000,000 g / mol. In another embodiment, the first-stage polymer has a weight-average molecular weight Mw of 50,000 g / mol to 1,000,000 g / mol, or 84,000 g / mol to 1,000,000 g / mol, or 300,000 g / mol to 750,000 g / mol, or 340,000 g / mol to 400,000 g / mol.

[0057] In one embodiment, the first-stage polymer contains polymerization units of acrylic acid monomer (AA) at 0.1 wt%, or 0.5 wt%, or 1.0 wt% to 1.5 wt%, or 2.0 wt%, or 3.0 wt%, or 5.0 wt%, or 10.0 wt% based on the dry weight of the first-stage polymer.

[0058] In one embodiment, the first-stage polymer contains polymerization units of 90 wt%, or 95 wt%, or 97 wt%, or 98 wt%, or 98.5 wt% to 99 wt%, or 99.5 wt%, or 99.9 wt% of a first vinyl monomer (such as EHA and / or MMA) based on the dry weight of the first-stage polymer.

[0059] In one embodiment, the first-stage polymer contains (i) polymerization units of 0.1 wt% to 10.0 wt%, or 0.5 wt% to 5.0 wt%, or 1.0 wt% to 2.0 wt% of an acrylic acid monomer (AA), and (ii) corresponding amounts of polymerization units of the first vinyl monomer (such as EHA and / or MMA), that is, 90.0 wt% to 99.9 wt%, or 95.0 wt% to 99.5 wt%, or 98.0 wt% to 99.0 wt% of the polymerization units of the first vinyl monomer based on the dry weight of the first-stage polymer, or consists essentially of, or consists of the same.

[0060] In one embodiment, the first-stage polymer contains (i) polymerization units of 0.1 wt% to 10.0 wt%, or 0.5 wt% to 5.0 wt%, or 1.0 wt% to 2.0 wt% of an acrylic acid monomer (AA), (ii) 60 wt%, or 70 wt%, or 75 wt%, or 80 wt% to 83 wt%, or 85 wt%, or 90 wt% of polymerization units of 2-ethylhexyl acrylate (EHA), and (iii) 9 wt%, or 10 wt%, or 15 wt%, or 16 wt% to 19 wt%, or 20 wt%, or 25 wt%, or 30 wt% of polymerization units of methyl methacrylate monomer (MMA) based on the dry weight of the first-stage polymer, or consists essentially of, or consists of the same. In a further embodiment, the first-stage polymer has a weight-average molecular weight Mw of 50,000 g / mol to 1,000,000 g / mol, or 84,000 g / mol to 1,000,000 g / mol, or 300,000 g / mol to 750,000 g / mol, or 340,000 g / mol to 400,000 g / mol.

[0061] (i) The total amount of AA and (ii) the first vinyl monomer is 100% by weight of the polymer in the first stage.

[0062] The polymer in the first stage may be composed of two or more embodiments disclosed herein.

[0063] ii. Polymer in the second stage The multi-stage latex polymer particles include a polymer in the second stage containing (i) a methacrylic acid monomer and (ii) a second vinyl monomer.

[0064] The polymer in the second stage contains a methacrylic acid monomer. The "methacrylic acid monomer" (or "MAA") is a compound having the following structure (3).

Chemical formula

[0065] The polymer in the second stage includes a second vinyl monomer. The second vinyl monomer can be any vinyl monomer disclosed herein other than MAA.

[0066] The second vinyl monomer is different from MAA. In other words, the second vinyl monomer is compositionally and / or structurally different from MAA.

[0067] The second vinyl monomer may be the same as or different from the first vinyl monomer in the polymer in the first stage. In one embodiment, the second vinyl monomer of the polymer in the second stage is the same as the first vinyl monomer of the polymer in the first stage. When the second vinyl monomer of the polymer in the second stage is the same as the first vinyl monomer of the polymer in the first stage, the second vinyl monomer and the first vinyl monomer contain the same vinyl monomer or a blend of the same vinyl monomers in the same weight ratio. In another embodiment, the second vinyl monomer of the polymer in the second stage is different from the first vinyl monomer of the polymer in the first stage.

[0068] In one embodiment, the second vinyl monomer is selected from EHA, MMA, and combinations thereof. In a further embodiment, the second vinyl monomer is EHA.

[0069] In another embodiment, the second-stage polymer contains, consists essentially of, or consists of a second vinyl monomer that is (i) MAA and (ii) EHA.

[0070] In one embodiment, the soluble fraction of MSLPP has a weight-average molecular weight Mw of 200,000 g / mol, or 210,000 g / mol to 248,000 g / mol, or 250,000 g / mol, or 275,000 g / mol, or 300,000 g / mol, or 400,000 g / mol, or 500,000 g / mol. In another embodiment, the soluble fraction of MSLPP has a weight-average molecular weight Mw of 200,000 g / mol to 500,000 g / mol, or 200,000 g / mol to 250,000 g / mol, or 210,000 g / mol to 248,000 g / mol. Without wishing to be bound by any particular theory, when the Mw of the soluble fraction of MSLPP is 90 wt% or more of the total polymer, it is considered to be a measured value of the representative Mw of the entire polymer.

[0071] In one embodiment, the second-stage polymer contains 0.1 wt%, or 1 wt%, or 2 wt%, or 4 wt% to 10 wt%, or 11 wt%, or 15 wt%, or 20 wt% of polymerization units of MAA based on the dry weight of the second-stage polymer.

[0072] In one embodiment, the second-stage polymer contains 80 wt%, or 85 wt%, or 89 wt%, or 90 wt% to 96 wt%, or 98 wt%, or 99 wt%, or 99.9 wt% of polymerization units of a second vinyl monomer (such as EHA) based on the dry weight of the second-stage polymer.

[0073] In one embodiment, the second-stage polymer contains, consists essentially of, or consists of (i) polymerization units of MAA in an amount of 0.1 wt% to 20 wt%, or 0.1 wt% to 10 wt%, or 1 wt% to 10 wt%, and (ii) corresponding amounts of polymerization units of a second vinyl monomer (such as EHA), that is, based on the dry weight of the second-stage polymer, 80 wt% to 99.9 wt%, or 90 wt% to 99.9 wt%, or 90 wt% to 99 wt% of polymerization units of the second vinyl monomer. In a further embodiment, the soluble fraction of the MSLPP has a weight-average molecular weight Mw of 200,000 g / mol to 500,000 g / mol, or 200,000 g / mol to 250,000 g / mol, or 210,000 g / mol to 248,000 g / mol.

[0074] In one embodiment, the second-stage polymer lacks or is substantially free of acrylic acid monomer (AA).

[0075] In one embodiment, the second-stage polymer lacks or is substantially free of methyl methacrylate monomer (MMA).

[0076] In one embodiment, the second-stage polymer is formed in the absence of a chain transfer agent (CTA). Non-limiting examples of CTA include methyl-3-mercapto-propionate (MMP) and n-dodecyl mercaptan (n-DDM). The second-stage polymer formed in the presence of CTA contains CTA residues in an amount greater than 0 ppm based on the total dry weight of the second-stage polymer.

[0077] The second-stage polymer may be composed of two or more embodiments disclosed herein.

[0078] The first-stage polymer is bonded to the second-stage polymer. In one embodiment, the first-stage polymer is bonded to the second-stage polymer by a cross-linking reaction between at least one monomer in the first-stage polymer and at least one monomer in the second-stage polymer.

[0079] In one embodiment, the MSLPP contains 60 wt%, or 65 wt%, or 70 wt%, or 75 wt%, or 79 wt% to 90 wt%, or 95 wt% of the first-stage polymer based on the total dry weight of the MSLPP.

[0080] In one embodiment, the MSLPP contains 5 wt%, or 10 wt% to 21 wt%, or 25 wt%, or 30 wt%, or 35 wt%, or 40 wt% of the second-stage polymer based on the total dry weight of the MSLPP.

[0081] In one embodiment, the MSLPP contains, consists essentially of, or consists of (i) 60 wt% to 95 wt%, or 75 wt% to 95 wt%, or 79 wt% to 90 wt% of the first-stage polymer and (ii) a corresponding amount of the second-stage polymer, i.e., 5 wt% to 40 wt%, or 5 wt% to 25 wt%, or 10 wt% to 21 wt% of the second-stage polymer based on the total dry weight of the MSLPP.

[0082] In one embodiment, the MSLPP has a glass transition temperature Tg of -54°C, or -50°C, or -45°C to -44°C, or -40°C, or -35°C, or -30°C, or -20°C, or 0°C, or 10°C, or 20°C. In another embodiment, the MSLPP has a Tg of -54°C to -20°C, or -50°C to 0°C, or -54°C to -30°C, or -54°C to -40°C, or -54°C to -44°C, or -50°C to -44°C.

[0083] In one embodiment, the MSLPP is formed using seed growth. During seed growth, seed particles (either copolymer seed particles or oligomer seed particles) are included in the emulsion polymerization process that produces the first stage polymer. In one embodiment, there is a period during which no detectable polymerization occurs between the formation of the seed particles and the formation of the first stage polymer. In the formation of the first stage polymer, more than half (by weight, based on the weight of the first stage polymer) of the first stage polymer forms on the surface of the seed particles. The first stage polymer encapsulates or substantially encapsulates the seed particles. The seed particles can be prepared as described in USP8,686,096 (e.g., Examples 1 and 5 (Columns 19 and 20)) and USP7,829,626, the entire contents of which are incorporated herein by reference. In one embodiment, the seed particles are oligomer seed particles containing acrylic monomers. In a further embodiment, the seed particles are acrylic oligomer seed (AOS) particles containing butyl acrylate, n-dodecyl mercaptan, methyl methacrylate (MMA), and methacrylic acid (MAA).

[0084] (A) The MSLPP having a first stage polymer and (B) a second stage polymer excludes single-phase polymers such as polymers prepared in a single polymerization step. Instead, the MSLPP includes two different polymers having different monomers bonded to each other ((A) the first stage polymer contains AA and a first vinyl monomer, and (B) the second stage polymer contains MAA and a second vinyl monomer), while a conventional single-phase polymer includes a single polymer with the same monomers distributed throughout the polymer chain, so the MSLPP is structurally different from a conventional single-phase polymer.

[0085] The MSLPP may be composed of two or more embodiments disclosed herein.

[0086] B. Linear diamine base The adhesive composition contains a linear diamine base.

[0087] A "linear diamine base" is a compound having two amine groups, a linear structure, and a pH greater than 7.0. An "amine group" is a moiety having the following structure (4).

Chemical formula

[0088] Non-limiting examples of suitable amine groups include an amino group in which R 5 and R 6 are each hydrogen in structure (4).

[0089] The linear diamine base contains two, but exactly two, amine groups. In other words, the linear diamine base excludes compounds containing one amine group (monoamines, such as products available from Huntsman sold under the JEFFAMINE M series), and compounds containing three or more amine groups (triamines, such as products available from Huntsman sold under the JEFFAMINE T series).

[0090] The linear diamine base excludes compounds having a branched structure, such as branched diamines available from Huntsman sold under the JEFFAMINE D series and JEFFAMINE ED series.

[0091] In one embodiment, the linear diamine base is a polyetheramine. As used herein, a "polyetheramine" is a compound having the following structure (5).

Chemical formula

[0092] In one embodiment, in structure (5), y is from 1 to 10, or from 2 to 10, or from 1 to 3.

[0093] Non-limiting examples of suitable linear diamine bases that are polyetheramines include products available from Huntsman sold under the JEFFAMINE EDR series, such as JEFFAMINE EDR-148 and JEFFAMINE EDR-176.

[0094] In one embodiment, the linear diamine base has the following structure (6).

Chemical formula

[0095] Non-limiting examples of linear diamine bases having structure (6) include JEFFAMINE EDR-148 available from Huntsman.

[0096] In one embodiment, the linear diamine base has a pH of 7.0, or 8.0, or 9.0, or 10.0, or 11.0, or greater than 11.5 to 11.9, or 12.0, or 13.0, or 14.0. In another embodiment, the linear diamine base has a pH of 10.0 to 13.0, or 11.0 to 12.0.

[0097] In one embodiment, the linear diamine base has a molecular weight of 30 g / mol, or 35 g / mol, or from 37 g / mol to 44 g / mol, or 50 g / mol, or 75 g / mol, or 100 g / mol. In another embodiment, the linear diamine base has a molecular weight of from 30 g / mol to 100 g / mol, or from 30 g / mol to 50 g / mol, or from 37 g / mol to 44 g / mol.

[0098] In one embodiment, the linear diamine base is at 25 °C, 1 mm 2 / second, or 5 mm 2 / second, or from 8 mm 2 / second to 9 mm 2 / second, or 10 mm 2 / second, or 15 mm 2 It has a viscosity of / second. In another embodiment, the linear diamine base has a viscosity of 1 mm 2 / second to 15 mm 2 / second, or 5 mm 2 / second to 10 mm 2 / second, or 8 mm 2 / second to 9 mm 2 It has a viscosity of / second.

[0099] In one embodiment, the linear diamine base has a flash point of 100 °C, or 105 °C, or 110 °C, or 115 °C to 120 °C, or 125 °C, or 130 °C. In another embodiment, the linear diamine base has a flash point of 100 °C to 130 °C, or 105 °C to 125 °C, or 105 °C to 120 °C.

[0100] In one embodiment, the linear diamine base has structure (5), or further has structure (6), and the linear diamine base has (i) a pH of 10.0 to 13.0, or 11.0 to 12.0, and / or (ii) a molecular weight of 30 g / mol to 100 g / mol, or 37 g / mol to 44 g / mol, and / or (iii) at 25 °C, 1 mm 2 / second to 15 mm 2 / second, or 8 mm 2 / second to 9 mm 2 / second viscosity, and / or (iv) has one, several, or all of the characteristics of a flash point of 100 °C to 130 °C, or 105 °C to 120 °C.

[0101] The linear diamine base may be composed of two or more embodiments disclosed herein.

[0102] C. Ethoxylated surfactant The adhesive composition contains an ethoxylated surfactant.

[0103] The "ethoxylated surfactant" is an alcohol ethoxylate having the following structure (7). [Chemical] In the formula, m is 1 to 10, or 11, or 15, or 20, or 25, and n is 1 to 2, or 3, or 4, or 5.

[0104] In one embodiment, in structure (7), m is 1 to 25, or 1 to 10, or 10.

[0105] In one embodiment, in structure (7), n is 1 to 5, or 1 to 4.

[0106] "Ethoxylate" is a compound formed by reacting a fatty alcohol with ethylene oxide.

[0107] Non-limiting examples of suitable ethoxylated surfactants include, in structure (7), ethoxylated tridecyl alcohol where m is equal to 10. Non-limiting examples of ethoxylated tridecyl alcohol include LUTENSOL TDA-8 available from BASF.

[0108] In one embodiment, the ethoxylated surfactant has a molecular weight of 400 g / mol, or 450 g / mol, or 500 g / mol to 550 g / mol, or 600 g / mol, or 700 g / mol, or 800 g / mol. In another embodiment, the ethoxylated surfactant has a molecular weight of 400 g / mol to 800 g / mol, or 500 g / mol to 600 g / mol.

[0109] In one embodiment, the ethoxylated surfactant has a hydrophilic-lipophilic balance (HLB) of 10, or 11, or 12 to 13, or 14, or 15. In another embodiment, the ethoxylated surfactant has an HLB of 10 to 15, or 12 to 13.

[0110] In one embodiment, the ethoxylated surfactant is an ethoxylated tridecyl alcohol having one or both of the following characteristics: (i) a molecular weight of 400 g / mol to 800 g / mol, or 500 g / mol to 600 g / mol, and / or (ii) an HLB of 10 to 15, or 12 to 13.

[0111] The ethoxylated surfactant may be composed of two or more embodiments disclosed herein.

[0112] D. Optional Additives In one embodiment, the adhesive composition contains (A) MSLPP, (B) a linear diamine base, (C) an ethoxylated surfactant, and (D) one or more optional additives.

[0113] Non-limiting examples of suitable additives include bases (such as ammonium hydroxide), plasticizers, oils, stabilizers, antioxidants, pigments, dyes, anti-adhesion additives, polymer additives, defoamers, preservatives, thickeners, rheology modifiers, humectants, fillers, solvents, nucleating agents, surfactants, chelating agents, gelling agents, processing aids, cross-linking agents, neutralizing agents, flame retardants, fluorescent agents, compatibilizers, antibacterial agents, water, and combinations thereof.

[0114] In one embodiment, the adhesive composition contains a rheology modifier. Non-limiting examples of suitable rheology modifiers include non-ionic urethane rheology modifiers such as ACRYSOL RM-2020 available from The Dow Chemical Company. In one embodiment, the adhesive composition contains 0.01 wt%, or 0.05 wt%, or 0.10 wt% to 0.25 wt%, or 0.30 wt%, or 0.50 wt%, or 1.0 wt%, or 2.0 wt%, or 3.0 wt% of the rheology modifier based on the total weight of the composition.

[0115] The optional additives may be composed of two or more embodiments disclosed herein.

[0116] In one embodiment, the adhesive composition contains 90 wt%, or 95 wt%, or 97 wt% to 99 wt% of MSLPP based on the total weight of the adhesive composition.

[0117] In one embodiment, the adhesive composition contains 0.5 wt%, or 0.8 wt% to 2.0 wt%, or 3.0 wt%, or 4.0 wt%, or 5.0 wt% of a linear diamine base based on the total weight of the adhesive composition.

[0118] In one embodiment, the adhesive composition contains 0.01 wt%, or 0.05 wt%, or 0.09 wt% to 0.15 wt%, 0.20 wt%, or 0.50 wt%, or 0.75 wt%, or 1.0 wt% of an ethoxylated surfactant based on the total weight of the adhesive composition.

[0119] In one embodiment, the composition contains (A) 90 wt% to 99 wt%, or 95 wt% to 99 wt%, or 97 wt% to 99 wt% of MSLPP, (B) 0.5 wt% to 5.0 wt%, or 0.8 wt% to 3.0 wt%, or 0.8 wt% to 2.0 wt% of a linear diamine base, (C) 0.01 wt% to 1.0 wt%, or 0.05 wt% to 0.50 wt%, or 0.09 wt% to 0.15 wt% of an ethoxylated surfactant, and (D) optionally, 0.01 wt%, or 0.05 wt%, or 0.10 wt% to 0.25 wt%, or 0.30 wt%, or 0.50 wt%, or 1.0 wt%, or 2.0 wt%, or 3.0 wt% of an optional additive (such as a rheology modifier), and consists of, consists essentially of, or contains them.

[0120] In one embodiment, the adhesive composition has a pH of 7.0, or 7.5, or 8.0, or greater than 8.3 to 9.8, or 10.0, or 11.0, or 12.0. In another embodiment, the adhesive composition has a pH of 7.0 to greater than 12.0, or 8.0 to 10.0, or 8.3 to 9.8.

[0121] In one embodiment, the adhesive composition has shear for over 500 hours, or over 1000 hours, or over 1500 hours, or over 1700 hours. In another embodiment, the adhesive composition has shear for 500 hours, or 1000 hours, or 1500 hours, or 1700 hours to 3000 hours, or 3500 hours. In one embodiment, the adhesive composition has shear for over 1700 hours.

[0122] In one embodiment, the adhesive composition has one, several, or all of the following properties: (i) a pH of 7.0 to 12.0, or 8.0 to 10.0, or greater than 8.3 to 9.8, and / or (ii) shear for over 500 hours, or over 1000 hours, or over 1500 hours, or over 1700 hours, and / or (iii) a 90° peel strength (stainless steel) of 200 g / in, or 300 g / in, or 500 g / in, or 600 g / in, or 650 g / in to 900 g / in, or 1000 g / in, or 1500 g / in, and / or (iv) a 90° peel strength (HDPE) of 200 g / in, or 250 g / in, or 300 g / in to 450 g / in, or 500 g / in, or 750 g / in, or 1000 g / in, and / or (v) a loop tack (stainless steel) of 200 g / in, or 400 g / in, or 600 g / in, or 650 g / in to 800 g / in, or 900 g / in, or 1000 g / in, or 1500 g / in, and / or (vi) a loop tack (HDPE) of 200 g / in, or 300 g / in, or 350 g / in, or 360 g / in, or 400 g / in to 650 g / in, or 750 g / in, or 1000 g / in.

[0123] In one embodiment, the adhesive composition (A) MSLPP that is 90 wt% to 99 wt%, or 95 wt% to 99 wt%, or 97 wt% to 99 wt% based on the total weight of the adhesive composition, (i) Based on the total dry weight of MSLPP, it is the first-stage polymer of 60% to 95% by weight, or 75% to 95% by weight, or 79% to 90% by weight, and based on the dry weight of the first-stage polymer, it contains, consists essentially of, or consists of (a) 0.1% to 10.0% by weight, or 0.5% to 5.0% by weight, or 1.0% to 2.0% by weight of polymerized units of acrylic acid monomer (AA), (b) 60% by weight, or 70% by weight, or 75% by weight, or 80% to 83% by weight, or 85% by weight, or 90% by weight of polymerized units of 2-ethylhexyl acrylate monomer (EHA), and (c) 9% by weight, or 10% by weight, or 15% by weight, or 16% to 19% by weight, or 20% by weight, or 25% by weight, or 30% by weight of polymerized units of methyl methacrylate monomer (MMA), and has a weight-average molecular weight of 50,000 g / mol to 1,000,000 g / mol, or 84,000 g / mol to 1,000,000 g / mol, or 300,000 g / mol to 750,000 g / mol, or 340,000 g / mol to 400,000 g / mol, the first-stage polymer, (ii) Based on the total dry weight of MSLPP, it is the second-stage polymer of 5% to 40% by weight, or 5% to 25% by weight, or 10% to 21% by weight, and based on the dry weight of the second-stage polymer, it contains, consists essentially of, or consists of (a) 0.1% to 20% by weight, or 0.1% to 10% by weight, or 1% to 10% by weight of polymerized units of methacrylic acid monomer (MAA), and (b) 80% to 99.9% by weight, or 90% to 99.9% by weight, or 90% to 99% by weight of polymerized units of a second vinyl monomer (such as EHA), the second-stage polymer, and it contains, consists essentially of, or consists of, The soluble fraction of MSLPP has a weight-average molecular weight Mw of 200,000 g / mol to 500,000 g / mol, or 200,000 g / mol to 250,000 g / mol, or 210,000 g / mol to 248,000 g / mol, An MSLPP having a glass transition temperature Tg of -54°C to 20°C, or -50°C to 0°C, or -54°C to -30°C, or -54°C to -40°C, or -54°C to -44°C, or -50°C to -44°C, and (B) A linear diamine base having structure (5), or further structure (6), in an amount of 0.5 wt% to 5.0 wt%, or 0.8 wt% to 3.0 wt%, or 0.8 wt% to 2.0 wt% based on the total weight of the adhesive composition, having (i) a pH of 10.0 to 13.0, or 11.0 to 12.0, and / or (ii) a molecular weight of 30 g / mol to 100 g / mol, or 37 g / mol to 44 g / mol, and / or (iii) a viscosity at 25°C of 1 mm 2 / s to 15 mm 2 / s, or 8 mm 2 / s to 9 mm 2 / s, and / or (iv) a flash point of 100°C to 130°C, or 105°C to 120°C, and having one, several, or all of the above characteristics, and (C) An ethoxylated surfactant in an amount of 0.01 wt% to 1.0 wt%, or 0.05 wt% to 0.50 wt%, or 0.09 wt% to 0.15 wt% based on the total weight of the adhesive composition, being an ethoxylated tridecyl alcohol having (i) a molecular weight of 400 g / mol to 800 g / mol, or 500 g / mol to 600 g / mol, and / or (ii) an HLB of 10 to 15, or 12 to 13, and having one or both of the above characteristics, and (D) Optionally, an optional additive (such as a rheology modifier) in an amount of 0.01 wt%, or 0.05 wt%, or 0.10 wt% to 0.25 wt%, or 0.30 wt%, or 0.50 wt%, or 1.0 wt%, or 2.0 wt%, or 3.0 wt% based on the total weight of the adhesive composition, and containing, consisting essentially of, or consisting of them, The adhesive composition has one, several, or all of the following properties: (i) a pH of 7.0 to 12.0, or 8.0 to 10.0, or greater than 8.3 to 9.8, and / or (ii) shear for more than 500 hours, or more than 1000 hours, or more than 1500 hours, or more than 1700 hours, and / or (iii) a 90° peel strength (stainless steel) of 200 g / in to 1500 g / in, or 500 g / in to 1000 g / in, or 650 g / in to 900 g / in, and / or (iv) a 90° peel strength (HDPE) of 200 g / in to 1000 g / in, or 300 g / in to 750 g / in, or 300 g / in to 450 g / in, and / or (v) a loop tack (stainless steel) of 200 g / in to 1500 g / in, or 400 g / in to 1000 g / in, or 650 g / in to 800 g / in, and / or (vi) a loop tack (HDPE) of 200 g / in to 1000 g / in, or 300 g / in to 750 g / in, or 350 g / in to 650 g / in.

[0124] It is understood that in each of the adhesive compositions disclosed herein, including the aforementioned adhesive composition, the total of the components is 100% by weight.

[0125] The adhesive composition may be composed of two or more embodiments disclosed herein.

[0126] In one embodiment, an article comprising a substrate and the above adhesive composition can be prepared. The substrate is in contact with an aqueous composition.

[0127] E. Article The present disclosure provides an article. The article includes a substrate and a coating on the substrate. The coating contains an adhesive composition. The adhesive composition contains (A) multi-stage latex polymer particles, (B) a linear diamine base, and (C) an ethoxylated surfactant. The (A) multi-stage latex polymer particles include (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer. The first-stage polymer is bonded to the second-stage polymer.

[0128] The adhesive composition can be any of the adhesive compositions disclosed herein.

[0129] The article includes a substrate. An adhesive composition is on at least one surface of the substrate. Non-limiting examples of suitable substrates include films, sheets, fabrics, cardboard, and wood. In one embodiment, the composition forms a seal between at least one surface of a substrate and at least one surface of another substrate.

[0130] The substrate is a continuous structure having two opposing surfaces.

[0131] In one embodiment, the article includes a first substrate and a second substrate. A coating containing the adhesive composition is between the first substrate and the second substrate. The first substrate and the second substrate may be the same or different. In one embodiment, the first substrate and the second substrate are the same in that they have the same composition and the same structure.

[0132] In one embodiment, the first substrate and the second substrate are different from each other in composition and / or structure.

[0133] In one embodiment, a coating containing an adhesive composition is applied to the surface of a first substrate. Non-limiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and injecting. The coating containing the adhesive composition is brought into contact with the surface of a second substrate.

[0134] In one embodiment, the coating containing the adhesive composition has a coat weight of 0.5 mil, or 0.6 mil, or 0.7 mil to 0.9 mil, or 1.0 mil. In another embodiment, the coating containing the adhesive composition has a coat weight of 0.5 mil to 1.0 mil, or 0.7 mil to 0.9 mil.

[0135] In one embodiment, the adhesive composition is uniformly applied onto the surface of the first substrate to form a coating, and then the coating is brought into contact with the second substrate. "Uniform application" means a layer of the composition that is continuous (not intermittent) across the entire surface of the substrate and has the same or substantially the same thickness across the entire surface of the substrate. In other words, the adhesive composition uniformly applied to the substrate directly contacts the substrate surface and has the same spread as the substrate surface.

[0136] The adhesive composition and the first substrate are in direct contact with each other. As used herein, the term "in direct contact" means a layer configuration in which the substrate is positioned directly adjacent to the adhesive composition or coating, and there is no intervening layer or intervening structure between the substrate and the adhesive composition or coating. The adhesive composition is in direct contact with the surface of the first substrate. In one embodiment, the coating is in direct contact with the surface of the second substrate.

[0137] In one embodiment, the substrate is a multilayer film or laminate having a layer selected from a biaxially oriented polypropylene ("BOPP") layer, a polyester layer, an ethylene-based polymer layer, a polyethylene terephthalate (PET) layer, and combinations thereof. In a further embodiment, the substrate includes a BOPP layer.

[0138] In one embodiment, the first substrate is a PET film and the second substrate is a BOPP film. The PET film is in direct contact with the coating, and the BOPP film is in direct contact with the coating.

[0139] Since the BOPP film has a non-porous and non-polar surface, it is difficult to bond with conventional adhesive compositions. However, unexpectedly, an article comprising a substrate having a BOPP film, in direct contact with a coating comprising the present adhesive composition, which comprises (A) multistage latex polymer particles having (i) a first-stage polymer containing an acrylic acid monomer and a first vinyl monomer, and (ii) a second-stage polymer containing a methacrylic acid monomer and a second vinyl monomer, (B) a linear diamine base, and (C) an ethoxylated surfactant, has been found to exhibit sufficient adhesion as shown by shear over 500 hours. Shear over 500 hours is advantageous in adhesive applications (such as labels) because it indicates that the label adheres to the article (e.g., a plastic or glass bottle) at its original position on the article over the life of the article.

[0140] In one embodiment, the article includes a BOPP film substrate in direct contact with a coating containing an adhesive composition, and the article has (i) a coating containing the adhesive composition having a coat weight of 0.5 mil to 1.0 mil, or 0.7 mil to 0.9 mil, and / or (ii) the adhesive composition having a pH of 7.0 to greater than 12.0, or 8.0 to 10.0, or 8.3 to 9.8, and / or (iii) the adhesive composition having a shear of greater than 500 hours, or greater than 1000 hours, or greater than 1500 hours, or greater than 1700 hours, and / or (iv) a 90° peel strength (stainless steel) of 200 g / in to 1500 g / in, or 500 g / in to 1000 g / in, or 650 g / in to 900 g / in, and / or (v) a 90° peel strength (HDPE) of 200 g / in to 1000 g / in, or 300 g / in to 750 g / in, or 300 g / in to 450 g / in, and / or (vi) a loop tack (stainless steel) of 200 g / in to 1500 g / in, or 400 g / in to 1000 g / in, or 650 g / in to 800 g / in, and / or (vii) a loop tack (HDPE) of 200 g / in to 1000 g / in, or 300 g / in to 750 g / in, or 350 g / in to 650 g / in, having one, several, or all of these properties.

[0141] Non-limiting examples of suitable articles include labels, signs, and combinations thereof.

[0142] The article may be composed of two or more embodiments disclosed herein.

[0143] By way of example, and not limitation, some embodiments of the present disclosure will now be described in detail in the following examples.

Examples

[0144] The monomers and chain transfer agents used in the examples are shown in Table 1 below.

Table 1

[0145] A. Comparative Sample 1 Comparative Sample 1 (CS 1) is an aqueous composition containing single-stage latex polymer particles prepared by emulsion polymerization of 2-ethylhexyl acrylate (EHA), methyl methacrylate (MMA), styrene (STY), and acrylic acid (AA). CS 1 is a copolymer containing 80.8 wt% EHA, 16.3 wt% MMA, 1.9 wt% STY, and 1 wt% AA based on the total weight of the CS 1 copolymer.

[0146] CS 1 is prepared by forming a monomer mixture (CS ME 1) containing 80.8 wt% EHA, 16.3 wt% MMA, 1.9 wt% STY, and 1 wt% AA. Next, a homogeneous mixture is prepared using components such as the monomer mixture (CS ME 1), 22.2 wt% deionized (DI) water, and 0.24 wt% Siponate™ DS-4 (branched alkylbenzene sulfonate (22.5 wt% aqueous solution, sodium dodecylbenzenesulfonate)), 0.19 wt% Acrysol A-102 solution (available from The Dow Chemical Company having 30 wt% solids), 0.059 wt% sodium carbonate buffer, and 0.008 wt% Dequest™ 2016 solution (having 33 wt% solids of sodium 1-hydroxyethylidene-1,1-diphosphonate).

[0147] Prepare a glass kettle equipped with a stirrer, a heater, a reflux condenser, and a nitrogen sparge tube. Add 53.2 wt% of DI water to the kettle. Cover the contents of the kettle (53.2 wt% of DI water and 0.004 wt% 4-hydroxy-Tempo) with nitrogen and heat to 88 °C. Once the kettle reaches a temperature of 88 °C, add the kettle buffer solution (1.05 g of sodium carbonate containing 26.3 g of DI water), followed by 7.5 g of rinse water. Add the kettle surfactant mixed solution (3.22 g of Siponate™ DS-4 and 45 g of DI water) to the kettle, followed by a rinse solution of 7.5 g of DI water.

[0148] Add 3 wt% of the homogenized mixture to the kettle as a seed, followed by the first catalyst solution (5.55 g of ammonium persulfate (APS) and 18.8 g of DI water), followed by rinse water. The calculated expected exotherm is less than 5 °C over several minutes. After the exotherm begins, supply the homogenized mixture (at a feed rate of 14.3 g / min) and the co-fed catalyst solution (1.8 g of APS in 78.8 g of distilled water) (at a feed rate of 0.54 g / min) to the kettle for the first 10 minutes. After 10 minutes, increase the feed over 70 minutes to 28.5 g / min for the homogenized mixture and 1.07 g / min for the co-fed catalyst. Maintain the reaction temperature at 85 - 87 °C. Once the feed is complete, add all of the rinse solution (DI water used to wash the feed line). Hold the reaction at 85 - 87 °C for 15 minutes and then cool to 75 °C over 15 minutes. At a temperature of 75 °C, add the accelerator solution (0.027 g of FeSO 4、Add 0.027 g of VERSENE EDTA (ethylenediaminetetraacetic acid) and 3 g of DI water to a kettle, and then add a rinse solution of 3 g of DI water. Next, start the addition of the oxidizing agent (10.65 g of t-butyl hydroperoxide (t-BHP) in 52.5 g of water) at a feed rate of 1.3 g / min over 50 minutes, and start the addition of the unwanted feed (5.63 g of sodium formaldehyde sulfoxylate (SSF) in 67.5 g of DI water) at a feed rate of 1.46 g / min. During the addition, cool the reactor to less than 50 - 60 °C over 50 minutes. At a reactor temperature of less than 55 °C, start the supply of the neutralizing agent (9.12 g of ammonium hydroxide and 9 g of DI water) at a feed rate of 1.81 g / min and conduct for 10 minutes. Cool the batch to less than 40 °C and filter with a 100-mesh filter bag.

[0149] B. Samples 2 - 9 Samples 2 - 9 are each an aqueous composition containing multistage latex polymer particles prepared by emulsion polymerization.

[0150] Prepare the first monomer emulsion (ME 1) in the first flask. The components of the first monomer emulsion (ME 1) for Samples 2 - 9 are shown in Table 2 below.

[0151] Prepare the second monomer emulsion (ME 2) in the second flask. The components of the second monomer emulsion (ME 2) for Samples 2 - 9 are shown in Table 2 below.

[0152] Prepare the initiator emulsion (IE) in a separate vial by combining DI water (44 g) and ammonium persulfate (APS) (5.64 g). IE is emulsified for 5 minutes using a homogenizer at 5,000 rpm.

[0153] Prepare the buffer solution (BSol) in a separate vial by combining DI water (10 g) and sodium carbonate (0.73 g).

[0154] Add 31.6 wt% DI water, 1.8 wt% of 60 nm preform seeds (supplied by The Dow Chemical Company), and 8.7 wt% of 230 nm preform seeds (supplied by The Dow Chemical Company) to a kettle equipped with a stirrer, a heater, a reflux condenser, and a nitrogen purge tube. Adding preform seed particles at the start of the reaction eliminates fluctuations in the nucleation step. For example, the polymerization rate and particle size can be easily controlled. Seed polymerization also results in less reactor deposits, reduced pebbling, and a more stable latex. Furthermore, by carefully controlling the amount of seed used, a bimodal latex with reduced viscosity can be produced. Cover the kettle contents with nitrogen and heat to 91 °C. Next, add an initiator solution (containing 1.41 g of APS in 17.5 g of DI water) and BSol to the kettle and stir for 1 minute. Next, set the temperature of the kettle to 86 - 89 °C, supply ME 1 to the kettle at a rate of 12.3 g / min for 10 minutes at a temperature of 88 °C, and simultaneously supply IE to the kettle at a rate of 0.32 g / min. Maintain the temperature at 86 - 89 °C. After 10 minutes, increase the feed rate of ME 1 to 24.5 g / min and the simultaneous feed of IE increases to 0.64 g / min. As soon as ME 1 is completely added to the kettle, add the feed of ME 2 over the remaining 70 minutes of the feed. At the end of the feed, add all of the DI water rinse solution to the kettle. Cool the kettle to 75 °C and add 10.00 grams of 0.001% Fe 2+ solution (0.02 g of FeSO 4、 0.01 g of VERSENE EDTA, DI water) to the kettle. Next, chase the remaining monomer by supplying the t-BHP solution (3.14 g in 30 g of water) at a feed rate of 0.55 g / min and supplying the SSF solution (2.17 g of SSF in 30 g of DI water) over 1 hour at a rate of 0.54 g / min. Cool the kettle to less than 50 - 60 °C during the chase addition. Cool the batch to less than 40 °C and filter through a 50 mesh filter bag.

Table 2

[0155] The aqueous compositions obtained containing the multi-stage latex polymer particles of Samples 2 to 9 are shown in Table 3.

Table 3

[0156] C. Preparation of Adhesive Composition In addition to Comparative Sample 1 (CS 1) and the polymer particles of Samples 2 to 9 prepared as described above, the materials used to produce the adhesive composition are shown in Table 4 below.

Table 4

[0157] The Comparative Sample 1 (CS 1) and the polymer particles of Samples 2 to 9 prepared as described above are each measured into a plastic wide-mouth jar. A wetting agent (LUTENSOL TDA-8) is added to the jar while continuously mixing with an overhead mixer for 10 minutes. Next, a rheology modifier (ACRYSOL RM-2020) is added to the jar and mixed for an additional 10 minutes. Next, the mixture is neutralized with ammonium hydroxide (NH4OH) or a diamine base (JEFFAMINE D-230 or JEFFAMINE EDR-148).

[0158] The compositions of each comparative sample composition and example composition are shown in Table 5 below.

[0159] D. Coating The comparative samples (CS) and example compositions (Ex) in Table 5 are coated onto the surface of a 1.2-mil-thick polyethylene terephthalate (PET) film equipped with a slip layer (RAF HOSTAPHAN (trademark) 2 PROKN 1S.sil film available from Mitsubishi Polyester Film) using a 0.8-mil Bird (trademark) applicator. Next, the coating is brought into contact with a biaxially oriented polypropylene (BOPP) film (supplied by Griff Papers) having a thickness of 2.0 mils.

[0160] The wet drawdown is dried at 85°C for 5 minutes in a convection oven. Next, the comparative samples and the example compositions are coated at a coat weight of 20 grams per square meter (gsm). The comparative samples and the example compositions are acclimated overnight in a controlled temperature and humidity chamber (CTR) (at 23°C and 50% relative humidity) prior to the application test. The properties of the comparative samples and the example compositions are shown in Table 5.

[0161] As shown in Table 5, CS 4 is a comparative composition containing (A) single-stage latex polymer particles (CS 1), (B) a linear diamine base (JEFFAMINE EDR-148), and (C) an ethoxylated surfactant (LUTENSOL TDA-8), and lacking multi-stage latex polymer particles. CS 4 shows shear below 500 hours (234 hours), indicating that an article coated with the adhesive composition of CS 4 is not suitable for article applications such as labels that require sufficient adhesion between the label and a second article (such as a bottle).

[0162] As shown in Table 5, CS 6, CS 10, and CS 14 are each comparative compositions containing (A) multi-stage latex polymer particles having (i) a first-stage polymer containing acrylic acid (AA) and a first vinyl monomer, and a second-stage polymer containing methacrylic acid monomer (MAA) and a second vinyl monomer (EHA), (B) a non-linear diamine base (JEFFAMINE D-230), and (C) an ethoxylated surfactant (LUTENSOL TDA-8), and lacking a linear diamine base. CS 6, CS 10, and CS 14 each show shear below 500 hours (152.6 hours, 405.2 hours, and 174 hours, respectively), indicating that an article coated with the adhesive composition of CS 6, CS 10, and CS 14 is not suitable for article applications such as labels that require sufficient adhesion between the label and a second article (such as a bottle).

[0163] CS 16 to CS 18 are each a comparative composition containing: (A) multistage latex polymer particles having a first-stage polymer containing acrylic acid (AA) and a first vinyl monomer, and a second-stage polymer formed with a CTA (MMP or n-DDM) containing methacrylic acid monomer (MAA) and a second vinyl monomer (EHA); (B) a linear diamine base (JEFFAMINE EDR-148); and (C) an ethoxylated surfactant (LUTENSOL TDA-8). CS 16 to CS 18 each show shear below 500 hours (40.4 hours, 85.5 hours, and 23.4 hours respectively), indicating that articles coated with the adhesive compositions of CS 16 to CS 18 are not suitable for article applications such as labels that require sufficient adhesion between the label and a second article (such as a bottle).

Table 5

[0164] CS 19 and CS 20 are each a comparative composition containing: (A) multistage latex polymer particles having a first-stage polymer containing acrylic acid (AA) and a first vinyl monomer, and a second-stage polymer formed with a CTA (MMP or n-DDM) containing acrylic acid monomer (AA) and a second vinyl monomer (EHA); (B) a linear diamine base (JEFFAMINE EDR-148); and (C) an ethoxylated surfactant (LUTENSOL TDA-8). The second-stage polymers of CS 19 and CS 20 lack the methacrylic acid monomer (MAA). CS 19 and CS 20 each show shear below 500 hours (113 hours and 7.9 hours respectively), indicating that articles coated with the adhesive compositions of CS 19 and CS 20 are not suitable for article applications such as labels that require sufficient adhesion between the label and a second article (such as a bottle).

[0165] The applicant unexpectedly discovered that the adhesive compositions (Ex 7, Ex 8, Ex 11, Ex 12, and Ex 15) containing (A) multi-stage latex polymer particles having (i) a first-stage polymer containing acrylic acid (AA) and a first vinyl monomer, and a second-stage polymer containing methacrylic acid monomer (MAA) and a second vinyl monomer (EHA), (B) a linear diamine base (JEFFAMINE EDR-148), and (C) an ethoxylated surfactant (LUTENSOL TDA-8) favorably exhibit high shear for at least 500 hours, as shown in Table 5. Accordingly, an article coated with the adhesive composition of Ex 7, Ex 8, Ex 11, Ex 12, or Ex 15 is suitable for article applications such as labels that require sufficient adhesion between the label and a second article (such as a bottle).

[0166] Conventional adhesive applications typically exhibit an inverse relationship between shear and peel properties (peel strength and loop tack). In other words, as the shear of a typical adhesive composition increases, the peel strength and loop tack decrease. However, the applicant unexpectedly discovered that an adhesive composition (Ex 7, Ex 8, Ex 11, Ex 12, and Ex 15) containing (A) multi-stage latex polymer particles having a first-stage polymer containing acrylic acid (AA) and a first vinyl monomer, and a second-stage polymer containing methacrylic acid monomer (MAA) and a second vinyl monomer (EHA), (B) a linear diamine base (JEFFAMINE EDR-148), and (C) an ethoxylated surfactant (LUTENSOL TDA-8) advantageously exhibits high shear for at least 500 hours while maintaining a 90° peel strength and loop tack suitable for article applications. For example, a comparison of Ex 15 (containing MSLPP sample 4, a linear diamine base, and an ethoxylated surfactant) with CS 14 (containing MSLPP sample 4 and an ethoxylated surfactant but no linear diamine base) shows that Ex 15 exhibits a shear (over 1700 hours) more than 9 times that of CS 14 (174 hours), while advantageously showing a higher 90° peel strength and loop tack (for both stainless steel and HDPE substrates) than CS 14. The present disclosure is not limited to the embodiments and examples contained herein, and is particularly intended to include, to the extent applicable to the following claims, modified forms of those embodiments, including portions of embodiments and combinations of elements of different embodiments. This application also relates to the following aspects. (1) An adhesive composition comprising: (A) Multistage latex polymer particles, wherein: (i) The first-stage polymer contains a monomer of acrylic acid and a first vinyl monomer; a monomer of acrylic acid; a first vinyl monomer, and the first-stage polymer; (ii) A second-stage polymer bonded to the first-stage polymer, the second-stage polymer containing a monomer of methacrylic acid and a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer, and the multistage latex polymer particles; a monomer of methacrylic acid; a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer, and the second-stage polymer; (B) A linear diamine base; (C) An ethoxylated surfactant, and the adhesive composition. (2) The adhesive composition according to (1) above, wherein the first vinyl monomer is selected from the group consisting of 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof. (3) The adhesive composition according to (1) or (2) above, wherein the second vinyl monomer is 2-ethylhexyl acrylate. (4) The multistage polymer particles comprise: (i) The first-stage polymer, which is based on the dry weight of the first-stage polymer, and contains 0.1 wt% to 10 wt% of the polymerized units of the acrylic acid monomer, and the first vinyl monomer selected from 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof; Based on the dry weight of the first-stage polymer, 0.1 wt% to 10 wt% of the polymerized units of the acrylic acid monomer; The first vinyl monomer selected from 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof, and the first-stage polymer; (ii) The second-stage polymer, which is based on the dry weight of the second-stage polymer, and contains 0.1 wt% to 10 wt% of the polymerized units of the methacrylic acid monomer and the second vinyl monomer which is 2-ethylhexyl acrylate, and the adhesive composition according to any one of (1) to (3) above. Based on the dry weight of the second-stage polymer, 0.1 wt% to 10 wt% of the polymerized units of the methacrylic acid monomer; The second vinyl monomer which is 2-ethylhexyl acrylate, and the second-stage polymer; (5) The adhesive composition according to any one of (1) to (4) above, wherein the first-stage polymer has a weight average molecular weight Mw of 84,000 g / mol to 1,000,000 g / mol. (6) The adhesive composition according to any one of (1) to (5) above, wherein the multistage latex polymer particles have a glass transition temperature Tg of -50°C to 0°C. (7) The adhesive composition according to any one of (1) to (6) above, wherein the linear diamine base is a polyetheramine. (8) The adhesive composition according to any one of (1) to (7) above, wherein the linear diamine base has structure (6).

Chem.

Claims

1. An adhesive composition comprising: (A) Multistage latex polymer particles, wherein: (i) A first-stage polymer comprising 0.1% to 10% by weight of an acrylic acid monomer, based on the dry weight of the first-stage polymer, a first vinyl monomer; (ii) A second-stage polymer bonded to the first-stage polymer, the second-stage polymer comprising 0.1% to 10% by weight of a methacrylic acid monomer, based on the dry weight of the second-stage polymer, a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer, and the second-stage polymer does not contain a chain transfer agent (CTA); (B) A linear diamine base; and (C) An ethoxylated surfactant.

2. The adhesive composition according to claim 1, wherein the first vinyl monomer is selected from the group consisting of 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof.

3. The adhesive composition according to claim 1 or 2, wherein the second vinyl monomer is 2-ethylhexyl acrylate.

4. The multistage latex polymer particles comprise: (i) The first-stage polymer comprising 0.1% to 10% by weight of a polymerization unit of the acrylic acid monomer, based on the dry weight of the first-stage polymer, the first vinyl monomer selected from 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof; (ii) The second-stage polymer comprising 0.1% to 10% by weight of a polymerization unit of the methacrylic acid monomer, based on the dry weight of the second-stage polymer, and the second vinyl monomer which is 2-ethylhexyl acrylate;

5. The adhesive composition according to any one of claims 1 to 4, wherein the first-stage polymer has a weight average molecular weight Mw of 84,000 g / mol to 1,000,000 g / mol.

6. The adhesive composition according to any one of claims 1 to 5, wherein the multistage latex polymer particles have a glass transition temperature Tg of -50°C to 0°C.

7. The adhesive composition according to any one of claims 1 to 6, wherein the linear diamine base is a polyetheramine.

8. The adhesive composition according to any one of claims 1 to 7, wherein the linear diamine base has structure (6). 【Chemical 1】

9. The adhesive composition according to any one of claims 1 to 8, wherein the ethoxylated surfactant contains ethoxylated tridecyl alcohol.

10. (A) 90% to 99% by weight of multi-stage latex polymer particles, (B) 0.1% to 1% by weight of a linear diamine base, (C) 0.01% to 1% by weight of an ethoxylated surfactant, comprising the adhesive composition according to any one of claims 1 to 9.

11. An article comprising a substrate contacted with the adhesive composition according to any one of claims 1 to 10.

12. An article, a substrate, a coating on the substrate, comprising the coating being (A) multi-stage latex polymer particles, wherein (i) the first-stage polymer, based on the dry weight of the first-stage polymer, 0.1% to 10% by weight of an acrylic acid monomer, a first vinyl monomer, comprising the first-stage polymer, (ii) the second-stage polymer bonded to the first-stage polymer, wherein the second-stage polymer, based on the dry weight of the second-stage polymer, 0.1% to 10% by weight of a methacrylic acid monomer, a second vinyl monomer, provided that the second vinyl monomer is different from the methacrylic acid monomer, and the second-stage polymer does not contain a chain transfer agent (CTA), comprising the second-stage polymer, (B) a linear diamine base, (C) an ethoxylated surfactant, comprising the article.

13. The article according to claim 12, wherein the first vinyl monomer is selected from the group consisting of 2-ethylhexyl acrylate, methyl methacrylate, and combinations thereof.

14. The article according to claim 12 or 13, wherein the second vinyl monomer is 2-ethylhexyl acrylate.

15. The article according to any one of claims 12 to 14, wherein the linear diamine base is a polyetheramine.

16. The article according to any one of claims 12 to 15, wherein the ethoxylated surfactant contains ethoxylated tridecyl alcohol.

17. ​ ​ The base material includes a biaxially oriented polypropylene film, and the article has a 90° peel (stainless steel) of 200 g / in (78.74 g / cm) to 1000 g / in (393.70 g / cm), and the 90° peel is measured according to PSTC 101, test method F. The article according to any one of claims 12 to 16.

18. The base material includes a biaxially oriented polypropylene film, the article has a loop tack (HDPE) of 200 g / in (78.74 g / cm) to 1000 g / in (393.70 g / cm), the loop tack is measured against a high density polyethylene (HDPE) substrate according to ASTM 6195-03, test method - A. The article according to any one of claims 12 to 17.

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