Primer compositions, adhesive systems, and related methods

Abstract

A primer composition, the primer composition comprising a polyacrylate dissolved or dispersed in water. The polyacrylate comprises at least (20) wt% of methyl methacrylate units, at least (15) wt% of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, at least (15) wt% of acrylic monomeric units having an alkyl group comprising at least four carbon atoms, and an acrylic monomer unit having a carboxylic acid group in an amount of 2.5 wt% to 10 wt%. A primer composition comprising a polymer dispersed in water and a solvent wherein the water comprises at least (50) wt% of the primer composition and the solvent comprises at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a dibasic ester. An adhesive system includes a primer composition and an adhesive tape. A method of making a bonded article is also described.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Application No. 63 / 521139, filed June 15, 2023, the disclosure of which is incorporated herein by reference in its entirety. Background Technology

[0003] Some tapes offer very high bond strength to a variety of clean substrates. In some cases, a primer can be applied prior to bonding to ensure maximum bond strength, which is desirable for certain applications.

[0004] U.S. Patent No. 10,640,656 (Moren et al.) describes a primer composition that provides adhesion between, for example, various substrates and double-sided tapes. U.S. Patent Nos. 9,234,122 (Schümann et al.), 9,080,083 (Schümann et al.), and 10,513,634 (Dietze et al.), and U.S. Patent Application Publications 2014 / 0113070 (Schümann et al.), 2017 / 0066947 (Dietze et al.), and 2017 / 0298230 (Schümann et al.) describe primer compositions comprising acrylate copolymers. U.S. Patent No. 10,385,159 (Urbach et al.) discloses a water-based primer composition for polycarbonate and polycarbonate blends. Summary of the Invention

[0005] This disclosure provides a composition that can be used as a primer, for example, for adhesive tapes. The primer composition comprises a polymer and water. The water-based nature of the primer composition makes it suitable for a variety of applications. Although water-based, the primer composition provides improved adhesion to a variety of substrates, as illustrated in the following examples. Advantageously, heat or radiation and reactive chemicals are not required in the primer or adhesive tape to provide beneficial adhesive properties.

[0006] In one aspect, this disclosure provides a primer composition comprising a polyacrylate dissolved or dispersed in water. The polyacrylate comprises at least 20% by weight of methyl methacrylate units based on the total weight of the monomer units in the polyacrylate, at least 15% by weight of monomer units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, at least 15% by weight of acrylic monomer units comprising an alkyl group having at least four carbon atoms, and an amount of 2.5% to 10% by weight of acrylic monomer units comprising a carboxylic acid group.

[0007] In another aspect, the present disclosure provides a primer composition comprising a polymer and a solvent dispersed in water, wherein water comprises at least 50 wt% of the primer composition. The solvent comprises at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a diester.

[0008] In another aspect, the present disclosure provides use of the above composition as a primer for an adhesive tape.

[0009] In another aspect, the present disclosure provides an adhesive system comprising a primer composition and an adhesive tape. The primer is not typically a component of the adhesive tape. The adhesive tape can be a semi-structural adhesive tape.

[0010] In another aspect, the present disclosure provides a method of manufacturing a bonded article. The method comprises applying the above primer composition to a surface of a first substrate, and applying a semi-structural tape to the primer composition on the surface of the first substrate.

[0011] In another aspect, the present disclosure provides an article bonded with the adhesive system disclosed herein and / or manufactured by the method disclosed herein.

[0012] As used herein: “Alkyl groups” and the prefix “alk” have only C-C and C-H bonds and include straight chain and branched chain groups as well as cyclic groups. In some embodiments, unless otherwise indicated, alkyl groups have up to 30 carbons (in some embodiments, up to 20, 15, 12, 10, 8, 7, 6, or 5 carbons). Cyclic groups can be monocyclic or polycyclic and in some embodiments have from 3 to 10 ring carbon atoms and other alkyl substituents; As used herein, “aryl” and “aromatic” include carbocyclic aromatic rings or ring systems, e.g., having 1, 2, or 3 rings and optionally containing at least one heteroatom (e.g., O, S, or N) in the ring, which ring is optionally substituted with up to five substituents including one or more alkyl groups having up to 4 carbon atoms (e.g., methyl or ethyl), alkoxy groups having up to 4 carbon atoms, halo (i.e., fluorine, chlorine, bromine, or iodine), hydroxyl, or nitro groups, examples of which include phenyl, naphthyl, biphenyl, fluorenyl, and furanyl, thienyl, pyridyl, quinolyl, isoquinolyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl.

[0013] The terms “acrylic” and “polyacrylate” refer to both acrylic polymers, oligomers, and monomers and methacrylic polymers, oligomers, and monomers; The term "(meth)acryl" refers to acryl (also known in the art as acryloyl and acrylyl) and / or methacryl (also known in the art as methacryloyl and methacrylyl); and "Curing" refers to the making of polymer chains from one or more monomers.

[0014] The term "polymer" refers to a molecule having a structure comprising a plurality of repeating units that are actually or conceptually derived from one or more monomers. The term "monomer" refers to a low relative molecular mass molecule that can combine with other molecules to form a polymer. The term "polymer" includes homopolymers and copolymers and homopolymers or copolymers that can be formed in miscible blends, for example, by co-extrusion or by reaction. The term "polymer" includes random polymers, block polymers, graft polymers, and star polymers. The term "polymer" includes oligomers.

[0015] A "monomeric unit" of a polymer or oligomer is a segment of the polymer or oligomer that is derived from a single monomer.

[0016] The term "sulfonate-functional" is interchangeable with "sulfonate-substituted" and refers to a compound that is substituted with a sulfonic acid, a sulfonate salt, or both.

[0017] "Dispersed" refers to a heterogeneous mixture of discrete particles or droplets in water. Polymers dispersed in water include both emulsions and suspensions.

[0018] Terms such as "one," "a," "an," and "the" are not intended to refer to only a singular entity, but include the general class of which a specific example can be used for illustration. The terms "one," "a," "an," and "the" are used interchangeably with the term "at least one."

[0019] The phrase "comprising at least one of a list of items," followed by a list of items, means that at least one of any of the items in the list of items is included. The phrase "at least one of a list of items" followed by a list of items means any of the items in the list of items are included.

[0020] The term "crosslinking" refers to the linking together of polymers by covalent chemical bonds, typically via crosslinking molecules or groups, to form a network polymer. Crosslinked polymers are generally characterized by insolubility, but can be swellable in the presence of a suitable solvent. The term "crosslinking" includes partial crosslinking.

[0021] Unless otherwise indicated, all numerical ranges are inclusive of their endpoints and non-integral values therebetween (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0022] The features and advantages of the present disclosure will be further understood upon consideration of the detailed description and attached claims, in conjunction with the accompanying figures. DETAILED DESCRIPTION

[0023] The present disclosure provides a primer composition comprising a polyacrylate composed of monomeric units. The polyacrylate comprises at least 20 weight % of methyl methacrylate monomeric units, based on the total weight of monomeric units in the polyacrylate. In some embodiments, the primer composition comprises at least 20, 21, 22, 23, 24, or 25 weight % of methyl methacrylate monomeric units, based on the total weight of monomeric units in the polyacrylate. In some embodiments, the primer composition comprises 21, 22, 23, 24, or 25 (wt %) to 65, 20 to 60, 20 to 40, or 40 to 60 weight % of methyl methacrylate, based on the total weight of monomeric units in the polyacrylate. Methyl methacrylate is commercially available from multiple suppliers, including under the trade designation “VISIOMER MMA” from Evonik Performance Materials GmbH.

[0024] The polyacrylate useful in some embodiments of the primer composition of the present disclosure comprises at least 15 weight % of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, based on the total weight of monomeric units in the polyacrylate. In some embodiments, the monomeric units comprise at least one of a tertiary amine or a tertiary amide. In some embodiments, the monomeric units comprise at least one of a secondary amine or a tertiary amine. In some embodiments, the monomeric units comprising at least one of a secondary amine or a tertiary amine are represented by Formula I:

[0025] wherein R1is hydrogen, alkyl, or aralkyl; R2is alkyl or aralkyl; or R1and R2together with the nitrogen atom to which they are attached form a 5-, 6-, or 7-membered ring; V is alkylene or aralkylene; W is -O- or -N(R3)-; R3is hydrogen, alkyl, aryl, alkylarylene, or aralkylene; and R is hydrogen or methyl. In some embodiments, R1is hydrogen, and R2is alkyl having up to four carbon atoms. In some embodiments, each of R1and R2is independently alkyl having up to four carbon atoms. In some embodiments, each of R1and R2is methyl. In some embodiments, W is -O- or -N(H)-. In some embodiments, W is -O-. In some embodiments, V is alkylene. In some embodiments, V is ethylene, propylene, or butylene. In some embodiments, V is ethylene.

[0026] In some embodiments, the monomer units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide are N-acryloylpiperidine units, N-methacryloylpiperidine units, or piperazine units represented by Formula II:

[0027] wherein R3is hydrogen, alkyl, aralkyl, or alkylcarbonyl; and R is hydrogen or methyl. In some embodiments, the monomer units comprising a tertiary amide include at least one of N-vinyl-2-pyrrolidinone units, N-vinylpiperidinone units, or N-vinylcaprolactam units. Combinations of any of these units can be useful.

[0028] In some embodiments, the monomer units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide include units of at least one of 2-(N,N- dimethylaminoethyl) (meth)acrylate, 2-(N,N-diethylaminoethyl) (meth)acrylate, 2-(tert- butylaminoethyl) (meth)acrylate, 2-(N,N-dimethylaminoethyl) (meth)acrylamide, 2-(N,N- diethylaminoethyl) (meth)acrylamide, 2-(tert-butylaminoethyl) (meth)acrylamide, N- (meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidinone. In some embodiments, the monomer units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide include units of at least one of 2-(N,N-dimethylaminoethyl) (meth)acrylate or N-vinyl-2-pyrrolidinone. In some embodiments, these monomer units include units of at least one of 2-(N,N-dimethylaminoethyl) methacrylate or 2-(N,N-dimethylaminoethyl) acrylate.

[0029] In some embodiments, the primer composition comprises at least 16, 17, 18, 19, or 20 weight percent, based on the total weight of monomeric units in the polyacrylate, of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide. In some embodiments, the primer composition comprises 15, 16, 17, 18, 19, or 20 to 40 weight percent, based on the total weight of monomeric units in the polyacrylate, of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide.

[0030] The polyacrylate useful in some embodiments of the primer compositions of the present disclosure comprises at least 15 weight percent, based on the total weight of monomeric units in the polyacrylate, of acrylic monomeric units comprising an alkyl group having at least four carbon atoms. The alkyl group of the alkyl acrylate or alkyl methacrylate can be linear, branched, or cyclic (including polycyclic) and can have 4 to 24, 4 to 18, or 4 to 12 carbon atoms. Examples of suitable acrylic monomeric units comprising an alkyl group having at least four carbon atoms include units of n-butyl acrylate, isobutyl acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, iso-pentyl (meth)acrylate, n-hexyl (meth)acrylate, iso-hexyl (meth)acrylate, octyl (meth)acrylate, iso-octyl (meth)acrylate, 2-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl acrylate, undecyl (meth)acrylate, n-dodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, n-nonyl (meth)acrylate, iso-nonyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. Suitable monomeric units further include units of mixtures of at least two or at least three structural isomers of secondary alkyl (meth)acrylates of Formula III:

[0031] wherein R4and R5are each independently C1to C 30a saturated straight-chain alkyl group; the sum of the number of carbon atoms in R4and R5is 7 to 31 ; and R6is H or CH3. In some embodiments, the sum of the number of carbons in R4and R5may be 7 to 27, 7 to 25, 7 to 21, 7 to 17, 7 to 11, 7, 11 to 27, 11 to 25, 11 to 21, 11 to 17, or 11. Methods for making and using such monomers and monomer mixtures are described in U.S. Patent No. 9,102,774 (Clapper et al.). In some embodiments, the acrylic monomer units comprising an alkyl group having at least four carbon atoms comprise units of at least one of 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isooctyl (meth)acrylate. In some embodiments, the acrylic monomer units comprising an alkyl group having at least four carbon atoms comprise units of 2-ethylhexyl acrylate or 2-isooctyl acrylate.

[0032] In some embodiments, the primer composition comprises at least 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt% of acrylic monomer units comprising an alkyl group having at least four carbon atoms, based on the total weight of monomer units in the polyacrylate. In some embodiments, the primer composition comprises 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt% to 50 wt%, 20 wt% to 40 wt%, 15 wt% to 45 wt%, 15 wt% to 30 wt%, or 30 wt% to 50 wt% of acrylic monomer units comprising an alkyl group having at least four carbon atoms, based on the total weight of monomer units in the polyacrylate.

[0033] The polyacrylate useful in the primer compositions of the present disclosure comprises 2.5 wt% to 10 wt% of acrylic monomer units comprising a carboxylic acid group. Examples of suitable acrylic monomers that comprise a carboxylic acid group to provide these monomer units include methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, ethyl acrylic acid, crotonic acid, citraconic acid, cinnamic acid, beta-carboxyethyl acrylate, and beta-methylacryloyloxyethyl hydrogen succinate. In some embodiments, the acrylic monomer units comprising a carboxylic acid group are acrylic monomer units or methacrylic monomer units, in some embodiments, acrylic monomer units. In some embodiments, the acrylic monomer units comprising a carboxylic acid group are present in the polyacrylate in an amount of 3 wt% to 9 wt%, 3 wt% to 8 wt%, or 3 wt% to 7 wt%, or 4 wt% to 6 wt%, based on the total weight of monomer units in the polyacrylate.

[0034] In some embodiments, the polyacrylate comprises additional acrylic monomer units. In some embodiments, the methyl methacrylate units, the monomer units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, the acrylic monomer units comprising an alkyl group having at least four carbon atoms, and the acrylic monomer units comprising a carboxylic acid group collectively comprise at least 95, 96, 97, 98, 99, or 100 percent by weight of the monomer units in the polyacrylate. In some embodiments, the polyacrylate is free of acrylic monomer units comprising a hydroxyl group, or contains no more than 0.5, 0.1, 0.05, 0.01, or 0.005 percent by weight of acrylic monomer units comprising a hydroxyl group based on the total weight of monomer units in the polyacrylate. In some embodiments, the polyacrylate is free of N-methylol acrylamide units and N-methylol methacrylamide units, or contains no more than 0.5, 0.1, 0.05, 0.01, or 0.005 percent by weight of N-methylol acrylamide units and N-methylol methacrylamide units based on the total weight of monomer units in the polyacrylate. In some embodiments, the polyacrylate is free of acrylic monomer units comprising a phosphate ester group, or contains no more than 0.5, 0.1, 0.05, 0.01, or 0.005 percent by weight of acrylic monomer units comprising a phosphate ester group based on the total weight of monomer units in the polyacrylate. In some embodiments, the polyacrylate is free of crosslinking monomer units or contains no more than 0.5, 0.1, 0.05, 0.01, or 0.005 percent by weight of crosslinking monomer units based on the total weight of monomer units in the polyacrylate, including any of those crosslinking monomer units described below in connection with adhesive tapes.

[0035] In some embodiments, the make film composition of the present disclosure and / or that can be used in the adhesive systems of the present disclosure comprises a polyamide. In some embodiments, the polyamide comprises an ionic group. In some embodiments, the polyamide comprises a reaction product of components including a dimer acid, an oxyalkylene diamine, an additional diamine comprising at least one of a primary diamine or a secondary diamine, and a sulfonate-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylate ester, or a diamine. In some embodiments, at least one second dimer acid is included in the components used to make the reaction product. It will be understood that the term “acid” is used herein to encompass diesters when referring to components for the reaction product, as both groups react with the amine to form an amide linkage. The difference is that an acid reacts with the amine to form an amide linkage and water byproduct, while an ester reacts with the amine to form an amide linkage and the corresponding alcohol.

[0036] Dimer acids are dicarboxylic acids that are typically formed by dimerizing one or more unsaturated fatty acids. In some embodiments, the dicarboxylic dimer acids can comprise at least one alkyl or alkenyl group, and can contain from 12 to 100 carbon atoms, from 16 to 100 carbon atoms, from 18 to 100 carbon atoms, from 20 to 100 carbon atoms, from 30 to 100 carbon atoms, from 12 to 80 carbon atoms, from 20 to 80 carbon atoms, from 30 to 80 carbon atoms, from 12 to 60 carbon atoms, from 20 to 60 carbon atoms, or from 30 to 60 carbon atoms, and are characterized by having two carboxylic acid groups. The dimer acids can be saturated or unsaturated. In some embodiments, the dimer acid can be a dimer of a fatty acid. As used herein, the phrase “fatty acid” means an organic compound composed of an alkyl group or an alkenyl group containing from 5 to 22 carbon atoms, and is characterized by having a terminal carboxylic acid group. Useful fatty acids are disclosed in “Fatty Acids in Industry: Processes, Properties, Derivatives, Applications,” Chapter 7, pp. 153-175, Marcel Dekker, Inc., 1989. In some embodiments, the dimer acid can be formed from dimerization of an unsaturated fatty acid having 18 carbon atoms, such as oleic acid or tall oil fatty acid. In some embodiments, the dimer acid is at least partially unsaturated and contains 36 carbon atoms. The dimer acid can have a relatively high molecular weight, and consists of a mixture comprising various ratios of a plurality of large or relatively high molecular weight substituted cyclohexene carboxylic acids, primarily 36-carbon dicarboxylic dimer acids. The component structures can be acyclic, cyclic (mono- or bi-cyclic), or aromatic, as shown in International Patent Application Publication PCT / IB2022 / 060487 (Kalgutkar et al.).

[0037] Dimer acids can be prepared by condensing unsaturated monofunctional carboxylic acids such as oleic acid, linoleic acid, soybean acid, or tall oil acid through their olefinic unsaturation in the presence of a catalyst such as an acidic clay. The distribution of various structures in the dimer acid (nominally a C36 diacid) depends on the unsaturated acid used in its manufacture. Typically, oleic acid produces a dicarboxylic dimer acid containing about 38% acyclic compounds, about 56% monocyclic and bicyclic compounds, and about 6% aromatic compounds. Soybean acid produces a dicarboxylic dimer acid containing about 24% acyclic compounds, about 58% monocyclic and bicyclic compounds, and about 18% aromatic compounds. Tall oil acid produces a dicarboxylic dimer acid containing about 13% acyclic compounds, about 75% monocyclic and bicyclic compounds, and about 12% aromatic compounds. The dimerization process also produces trimer acids. In some embodiments, the dimer acid comprises less than 10 mol% of trimer acid content. Commercial dimer acid products are typically purified by distillation to produce a range of dicarboxylic acid content. Useful dimer acids contain at least 80% dicarboxylic acid, 90% dicarboxylic acid content, or at least 95% dicarboxylic acid content. For certain applications, it can be advantageous to further purify the dimer acid by color reduction techniques including hydrogenation of the unsaturated groups, as disclosed in U.S. Patent No. 3,595,887 (Kulkarni et al.). Hydrogenated dimer acids can also provide enhanced oxidative stability at elevated temperatures. Other useful dimer acids are disclosed in Kirk-Othmer Encyclopedia of Chemical Technology, Organic Chemicals: Dimer Acids (ISBN 9780471238966) Copyright © 1999-2014 John Wiley and Sons, Inc. Commercially available dicarboxylic dimer acids are available, for example, under the trade designations “RADIACID 970” and “RADIACID 959” from Oleon, Simpsonville, SC, and under the trade designations “PRIPOL 1006,” “PRIPOL 1009,” “PRIPOL 1013,” “PRIPOL 1017,” and “PRIPOL 1025” from Cargill Inc., Minneapolis, MN.

[0038] In some embodiments, the dimer acid has a number average molecular weight of at least 300 grams per mole (g / mol), 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 750 g / mol, or 800 g / mol; and not more than 1400 g / mol, 1350 g / mol, 1300 g / mol, 1250 g / mol, 1200 g / mol, 1150 g / mol, 1000 g / mol, 950 g / mol, 800 g / mol, 750 g / mol, or 700 g / mol. In some embodiments, the dimer acid has a number average molecular weight ranging from 300 g / mol to 1400 g / mol, 300 g / mol to 1200 g / mol, 300 g / mol to 1000 g / mol, or 300 g / mol to 800 g / mol. The number average molecular weight can be determined using gel permeation chromatography (GPC).

[0039] In some embodiments, the mole fraction of dimer acid, based on the total moles of the combination of dimer acid, any second diacid, and any sulfonate-functional monomer comprising at least one of a dicarboxylic acid or a dicarboxylic acid ester (e.g., the sum of all diacids) used to form the polyamide, is at least 0.40, 0.42, 0.45, 0.47, 0.50, 0.52, 0.55, 0.57, 0.60, 0.62, 0.65, 0.67, 0.70, 0.72, or 0.75; and not more than 0.99, 0.98, 0.97, 0.96, 0.95, 0.94, 0.93, 0.92, 0.91, 0.90, 0.87, 0.85, 0.82, 0.80, 0.77, 0.75, 0.72, 0.70, 0.67, 0.65, 0.62, or 0.60, based on the total moles of the combination of dimer acid, at least one second diacid, and any sulfonate-functional monomer comprising at least one of a dicarboxylic acid or a dicarboxylic acid ester. In some embodiments, the mole fraction of dimer acid can be from 0.40 to 0.99, 0.50 to 0.95, or 0.60 to 0.90, based on the total moles of the combination of dimer acid, any second diacid, and any sulfonate-functional monomer comprising at least one of a dicarboxylic acid or a dicarboxylic acid ester.

[0040] In some embodiments, the polyamide comprises the reaction product of components comprising a sulfonate-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic acid ester, or a diamine. Suitable sulfonate-functional monomers comprising at least one of a dicarboxylic acid or a dicarboxylic acid ester include sulfonate-substituted phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, esters thereof, and combinations thereof. The counterion of the sulfonate can be H+or other metal ions such as potassium, lithium, zinc, magnesium, calcium, cobalt, iron, and / or antimony. In some embodiments, the sulfonate-functional monomer comprises an aryl group (e.g., phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, esters thereof, and combinations thereof). Suitable sulfonate-functional monomers include 5-sulfoisophthalic acid sodium salt (i.e., sodium isophthalic acid sulfonate (SSIP)) and those represented by Formula IV:

[0041] where M+is ammonium, sodium, lithium, or potassium, an example of which is the sodium salt of dimethyl 5-sulfoisophthalate (DMSSIP). Sulfonate-functional isophthalic and terephthalic acids and esters thereof are described in detail in U.S. Patent No. 3,389,549 (David).

[0042] Suitable sulfonate-functional diamines include N-(sulfoalkyl)alkylenediamines such as those having the formula H2N-R7-NH-(CH2) y -SO3 - Y + where R7is an alkylene group having 2 to 16 carbon atoms, which can be linear, branched, cyclic, or combinations thereof, y is an integer from 4 to 6, and Y+is H or an alkali metal, and those represented by Formula V:

[0043] where n is a number from 0 to 6, each R8is independently selected from H and lower alkyl, and M+is selected from H, an ammonium group, a Group I alkali metal, and a Group II alkaline earth metal. In some cases, each R8is the same. Such sulfonate-functional diamines are described in detail in U.S. Patent Nos. 3,454,535 (Bodesheim et al.) and 3,184,436 (Magat).

[0044] In some embodiments, the mole fraction of the sulfonate-functional monomer is 0.01 to 0.20, based on the total moles of the dimer acid, any second dimer acid, and any combination of sulfonate-functional diacid or diester used to form the polyamide, or the oxyalkylenediamine, at least one second diamine, and any combination of sulfonate-functional diamine used to form the polyamide. In some embodiments, the mole fraction of the sulfonate-functional monomer is at least 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or at least 0.10; and not more than 0.20, 0.19, 0.18, 0.17, 0.16, 0.15, 0.14, 0.13, 0.12, 0.11, or not more than 0.10.

[0045] In some embodiments, the polyamide comprises the reaction product of a component comprising an oxyalkylene diamine. In some embodiments, the oxyalkylene diamine is a polyoxyalkylene diamine comprising at least one of polyethylene oxide or polypropylene oxide. In some embodiments, the oxyalkylene diamine comprises both ethylene oxide units and propylene oxide units. Suitable oxyalkylene diamines include those commercially available under the trade designation “JEFFAMINE Ed” (including ED-600, ED-900, and ED-2003 having molecular weights of about 600 g / mol, 900 g / mol, and 2000 g / mol, respectively) from Huntsman Corporation (The Woodlands, TX), as well as PPG-based diamines commercially available under the trade designation “BAXXODUR EC” (e.g., EC 301, EC 302, and EC 303) from BASF (Florham Park, New Jersey) and under the trade designation “JEFFAMINE D” from Huntsman Corporation.

[0046] In some embodiments, the molar fraction of the oxyalkylene diamine is 0.005 to 0.10, 0.01 to 0.03, based on the total moles of the combination of oxyalkylene diamines, the at least one second diamine, and any sulfonate diamine used to form the polyamide (e.g., the sum of all diamines). In some embodiments, the molar fraction of the oxyalkylene diamine is at least 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, 0.012, 0.015, 0.017, 0.020, 0.022, 0.025, 0.027, 0.030, 0.032, 0.035, 0.037, 0.040, 0.042, 0.045, 0.047, 0.050, 0.052, 0.055, 0.057, or at least 0.060, based on the total moles of the combination of oxyalkylene diamines, the at least one second diamine, and any sulfonate-functional diamine; and no greater than 0.100, 0.095, 0.090, 0.085, 0.080, 0.075, 0.070, 0.065, 0.060, 0.055, 0.050, 0.045, 0.040, 0.035, 0.030, or no greater than 0.025.

[0047] In some embodiments, the molar ratio of the oxyalkylene diamine to the sulfonate- functional monomer is 1 : 10 to 2: 1, 1 :6.66 to 1 : 1, or 1 :5 to 1 :2. When the molar ratio of the oxyalkylene diamine to the sulfonate-functional monomer is lower than 1 : 10, the dispersion tends to contain large particles, and when the ratio is much higher than 2: 1, the dispersion can have the consistency of a hand soap (e.g., a lotion).

[0048] In some embodiments, the polyamide comprises the reaction product of a component comprising at least one second diamine. The "at least one second diamine" is in addition to and different from the oxyalkylene diamines and the sulfonate-functional diamines described above. The at least one second diamine can be a combination of two or more different diamines (e.g., two diamines, three diamines, or four diamines). The at least one second diamine can be one or more secondary diamines, one or more secondary / primary mixed diamines, one or more primary diamines, or a combination thereof. The at least one second diamine comprises an alkyl group, an alkylene group, an aryl group, a cycloalkyl group, or any combination thereof. In some embodiments, the at least one second diamine comprises a linear or branched aliphatic diamine and a cycloaliphatic diamine. In some embodiments, the number average molecular weight of the at least one second diamine can be 30 g / mol to 5000 g / mol, 30 g / mol to 500 g / mol, or 50 g / mol to 100 g / mol.

[0049] In some embodiments, the at least one second diamine is represented by the formula R10-NH-R9-NH-R10, where R9 is an arylene group or an alkylene group, where the alkylene group can be linear, branched, cyclic, or a combination thereof, and can be interrupted by at least one -O-, heterocycle, or arylene group, and each R10 is independently hydrogen, aryl, arylalkylene, or alkyl, where the alkyl group can be linear, branched, cyclic, or a combination thereof, and can be interrupted by at least one -O-, or where the R10 groups are joined together to form an alkylene group as part of a ring. In some embodiments, R9 is an alkylene group having 2 to 16, 2 to 6, or 2 to 4 carbon atoms. Examples of suitable alkylene groups include -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -cyclohexylene-CH2-cyclohexylene, -CH2CH2-O-CH2CH2-, and -CH2-furan ring-CH2-. An example of a suitable arylene group includes 1,4-phenylene. In some embodiments, each R10 is an alkyl group having 2 to 8, 2 to 6, or 2 to 4 carbon atoms. Examples of suitable alkyl groups include methyl, ethyl, isopropyl, cyclohexyl, ethoxymethyl, and methoxyethyl. Examples of suitable aryl groups include phenyl and pyridyl.

[0050] In some embodiments, neither R10 group is a hydrogen atom. That is, the diamine can have two secondary amino groups and can be referred to as a secondary diamine, or have one primary amino group and one secondary amino group and can be referred to as a secondary / primary mixed diamine. Examples of suitable secondary diamines include piperazine, 1,3-bis-4-piperidinylpropane, 4,4'-methylenebis[N-sec- butylaniline], and 4,4'-methylenebis[N-(l-methylpropyl)cyclohexylamine. An example of a suitable secondary / primary mixed diamine includes 2-aminoethylpiperazine. In some embodiments, there is no secondary / primary mixed diamine. In some embodiments, there is a secondary / primary mixed diamine such that the mole fraction of secondary / primary mixed diamine is less than 0.50 or no greater than 0.40, 0.30, 0.20, 0.10, or 0.05 based on the total moles of at least one second diamine. In some embodiments, both R10 groups are hydrogen atoms, and the diamine can be referred to as a primary diamine. Examples of suitable primary amines include ethylenediamine, m-xylylenediamine, 1,6-hexanediamine, o-toluidine, or 1,3-xylylenediamine.

[0051] In some embodiments, the mole fraction of the at least one second diamine is 0.70 to 0.995, based on the total moles of the combination of oxyalkylenediamines used to form the polyamide, the at least one second diamine, and any sulfonate-functional diamine (e.g., the sum of all diamines). In some embodiments, the mole fraction of the at least one second diamine is at least 0.700, 0.710, 0.720, 0.730, 0.740, 0.750, 0.760, 0.770, 0.780, 0.790, 0.800, 0.810, 0.820, 0.830, 0.840, 0.850, 0.860, 0.870, 0.880, 0.890, 0.900, 0.905, 0.910, 0.915, 0.920, 0.925, 0.930, 0.935, 0.940, 0.945, 0.950, 0.955, or at least 0.960, based on the total moles of the combination of oxyalkylenediamines used to form the polyamide, the at least one second diamine, and any sulfonate-functional diamine; and not more than 0.995, 0.995, 0.990, 0.985, 0.980, 0.975, 0.970, 0.965, 0.960, 0.955, 0.950, 0.945, 0.940, 0.935, 0.930, 0.910, 0.890, 0.870, 0.850, 0.830, 0.810, 0.790, 0.770, or not more than 0.750.

[0052] In some embodiments, the polyamide comprises the reaction product of a component comprising at least one second diacid. The "at least one second diacid" is in addition to and different from the aforementioned dimer acid and sulfonate-functional diacid or diester. Examples of suitable diacids include adipic acid, azelaic acid, sebacic acid (i.e., pimelic acid), dodecanedioic acid, 1,3-benzenedicarboxylic acid, 1,4- benzenedicarboxylic acid, and 11-aminoundecanoic acid. In some embodiments, the mole fraction of the at least one second diacid is 0 to 0.60, based on the total moles of the combination of dimer acid, at least one second diacid, and any sulfonate-functional diacid or diester used to form the polyamide. In some embodiments, the mole fraction of the at least one second diacid can be 0 (i.e., not present), or at least 0.01, 0.02, 0.05, 0.07, 0.10, 0.12, 0.15, 0.17, 0.20, 0.22, 0.25, 0.27, 0.30, 0.32, or 0.35; and not more than 0.60, 0.58, 0.57, 0.56, 0.55, 0.54, 0.53, 0.52, 0.51, 0.50, 0.47, 0.45, 0.42, 0.40, 0.37, 0.35, 0.32, 0.30, 0.27, 0.25, 0.22, or not more than 0.20, based on the total moles of the combination of dimer acid, at least one second diacid, and any sulfonate-functional diacid or diester used to form the polyamide.

[0053] In some embodiments, the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the sulfonate-functional monomer is 0.01 to 0.20, and the mole fraction of the at least one second diacid is 0 to 0.60, each based on the total moles of the combination of dimer acid, sulfonate-functional monomer, and at least one second diacid used to form the ionomeric polyamide, and the mole fraction of the oxyalkylene diamine is 0.005 to 0.10, and the mole fraction of the at least one second diamine is 0.70 to 0.995, each based on the total moles of the combination of oxyalkylene diamine, at least one second diamine, and any sulfonate-functional diamine used to form the ionomeric polyamide. It should be understood that the sum of all mole fractions for a particular group of components (e.g., diacids, diamines, etc.) will total 1.0.

[0054] Generally, the polymerizable composition is substantially free (e.g., lacks) diols, which results in a polyamide that is substantially free of ester linkages. The presence of ester linkages in the polymer generally decreases the thermal and hydrolytic stability of the polymer.

[0055] In some embodiments, the polymerizable composition useful for making the polyamide contains a 1.01 to 1.2 molar or 1.01 to 1.05 molar excess of the amine. In some embodiments, the polymerizable composition useful for making the polyamide contains an equimolar ratio (1 : 1) or a molar excess of the acid (e.g., 1.05: 1). A molar excess of the acid monomer will result in an acid-terminated polyamide, and a molar excess of the amine monomer will result in an amine-terminated polyamide. The use of a sulfonate-functional diamine can aid in the formation of an amine-terminated polyamide.

[0056] In some embodiments, the reaction product of the dimer acid, the oxyalkylene diamine, the additional diamine comprising at least one of a primary diamine or a secondary diamine, the sulfonate-functional monomer, and the optional second dimer acid is represented by Formula VI and Formula VII

[0057] wherein R11is independently a residue of a dimer acid at any of the above molar ratios (e.g., any of the above dimer acids) or a residue of a second dimer acid (e.g., any of the above at least one second dimer acid); R12is independently an oxyalkylene at any of the above molar ratios as described above in any of its embodiments or R9, R13is an alkylene, an arylene, or a combination thereof, and R10and M+are as defined above in any of its embodiments. In some embodiments, R13is an arylene.

[0058] In some embodiments, the polyamide has a glass transition temperature of no greater than 25°C, 20°C, 15°C, 10°C, 5°C, 0°C, -5°C, -10°C, -15°C, -20°C, -25°C, -30°C; and at least -50°C. The glass transition temperature is measured by differential scanning calorimetry using a 10 Kelvin / minute ramp rate.

[0059] The polyamide can be formed according to conventional condensation reactions between the dimer acid, the oxyalkylene diamine, the additional diamine comprising at least one of a primary diamine or a secondary diamine, the sulfonate-functional monomer, and the optional at least one second dimer acid. In some embodiments, the condensation reaction includes refluxing the polymerizable composition followed by distillation.

[0060] At least in view of U.S. Patent No. 3,709,865 (Lofquist et al.), it is unexpected that the polyamides as described herein can be successfully synthesized using the components described above, particularly the dimer acid that tends to be hydrophobic. It is further unexpected that the polyamides as described herein are suitable for use as a primer due to the predominantly hydrophobic nature of the polyamides.

[0061] In some embodiments, the make composition of the present disclosure comprises a polyurethane. The polyurethane can comprise a backbone of various suitable configurations. The backbone can optionally include one or more other backbone linkages (e.g., amide, ester, carbonate, epoxy, ether, imide, imine, or urea linkages, or combinations thereof). In addition, the backbone of the polyurethane polymer can optionally include one or more oligomer or polymer segments (e.g., acrylic, polyamide, polyester, poly(carbonate), epoxy, polyether, polyimide, polyimine, or polyurea segments, or combinations thereof). The polyurethane can be linear or substantially linear.

[0062] The polyurethane can be formed using any suitable reactants and any suitable method. The polyurethane is typically formed from starting materials including one or more isocyanates, one or more polyols, and optionally one or more additional reactants (e.g., having one or more active hydrogen groups). In some cases, the isocyanate is reacted in stoichiometric excess of the polyol. For example, the ratio of isocyanate groups to hydroxyl groups can be in the range of about 1.1 : 1 to 3: 1 (NCO:OH), about 1.2: 1 to 2.5: 1, or about 1.3: 1 to 2: 1. The polyurethane can have any suitable molecular weight, for example, a number average molecular weight of about 1,000 to about 10,000, or about 2,500 to about 7,500.

[0063] Suitable isocyanates include those having one, two, three, or four isocyanate groups and mixtures thereof. Suitable diisocyanates include isophorone diisocyanate (i.e., 5- isocyanato-l-isocyanatomethyl-l,3,3-trimethylcyclohexane); 5-isocyanato-l-(2- isocyanatoethyl-l-yl)-l,3,3-trimethylcyclohexane; 5-isocyanato-l-(3- isocyanatoprop-l-yl)-l,3,3-trimethylcyclohexane; 5-isocyanato-(4- isocyanatobut-l-yl)-l,3,3-trimethylcyclohexane; l-isocyanato-2-(3- isocyanatoprop-l-yl)cyclohexane; l-isocyanato-2-(3-isocyanatoethyl-l-yl)cyclohexane; l-isocyanato-2-(4-isocyanatobut-l-yl)cyclohexane; 1,2- diisocyanatocyclohexane; 1,3-diisocyanatocyclohexane; 1,4- diisocyanatocyclohexane; dicyclohexylmethane 2,4'-diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; pentamethylene diisocyanate; hexamethylene diisocyanate; ethylethylene diisocyanate; trimethylhexane diisocyanate; heptamethylene diisocyanate; 2-heptyl-3,4-bis(9-isocyanatononyl)-l-pentyl- cyclohexane; 1,2-, 1,4-, and 1,3-bis(isocyanatomethyl)cyclohexane; 1,2-, 1,4-, and 1,3-bis(2-isocyanatoethyl-l-yl)cyclohexane; 1,3-bis(3- isocyanatoprop-l-yl)cyclohexane; 1,2-, 1,4-, or 1,3-bis(4- isocyanatobut-l-yl)cyclohexane; liquid bis(4-isocyanatocyclohexyl)- methane; and derivatives or mixtures thereof. In some embodiments, the isocyanate or mixture of isocyanates is non-aromatic (e.g., aliphatic). In some embodiments, the isocyanate includes at least one of isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HMDI). In some embodiments, HMDI is the primary isocyanate used to make the polyurethane, in other words, there are more HMDI units than any other isocyanate unit.

[0064] Suitable polyols for making polyurethanes include monomeric, oligomeric, polymeric, and mixtures thereof, and include diols, triols, polyols having 4 or more hydroxyl groups, and mixtures thereof. Examples of polyols used as reactants or starting materials for oligomeric or polymeric polyols include ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, trimethylolpropane, trimethylolethane, tripropylene glycol, neopentyl glycol, pentaerythritol, 1,4-butanediol, hexanediol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol or polypropylene glycol, isopropylidene bis(p-phenylene-oxypropanol-2), and mixtures thereof. Examples of suitable oligomeric and / or polymeric polyols include polyether polyols, polyester polyols, polyether ester polyols, polyurea polyols, polyamide polyols, polycarbonate polyols, saturated or unsaturated polyolefin polyols, and combinations thereof. In some embodiments, the diol is a polyester diol. Useful polyester diols can include units of any of the above diols as well as units of aromatic diacids, aliphatic diacids, or combinations thereof. In some embodiments, the polyester diol includes units of a linear diol having 4 or more than 4 carbon atoms and units of a linear diacid having 4 or more than 4 carbon atoms. In some embodiments, the polyester diol further includes units of phthalic acid, isophthalic acid, or terephthalic acid.

[0065] In some embodiments, monomers or oligomers having salt groups or salt-forming groups can be included in the reactants used to produce the polyurethane, although this is not required. In some embodiments, acid or anhydride functional salt-forming monomers such as dimethylolpropionic acid or trimellitic anhydride are used to form the polyurethane. In some embodiments, the polyurethane includes acid or anhydride groups neutralized with a tertiary amine (or other neutralizable groups capable of forming an anionic salt group).

[0066] Some polyurethanes useful in the practice of the present disclosure are commercially available, for example, as emulsions from Alberdingk Boley and BASF.

[0067] The make coat compositions of the present disclosure and / or make coat compositions useful in the adhesive systems of the present disclosure include water. In some embodiments, water comprises at least 50%, 55%, 60%, 65%, 70%, or 75% by weight of the make coat composition. In some embodiments, water comprises no more than 95%, 92.5%, 90%, 87.5%, or 85% by weight of the make coat composition.

[0068] In some embodiments, the make compositions of the present disclosure and / or make compositions useful in the adhesive systems of the present disclosure comprise a solvent. In some embodiments, the solvent useful is non-flammable and has a low vapor pressure (e.g., less than 1 hundred pascal (hPa) at 20 °C). Examples of useful solvents for the make compositions include polar and / or water-miscible (i.e., soluble in water in all proportions) solvents, such as monohydric alcohols having 1 to 8 or more carbon atoms (e.g., methanol, ethanol, isopropanol, propanol, butanol, or isooctanol); polyols, such as diols (e.g., ethylene glycol or propylene glycol), terminal alkanediols (e.g., 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, or 1,8-octanediol), polyglycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, or poly(propylene glycol), triols (e.g., glycerol, trimethylolpropane), or pentaerythritol; polyol ethers (e.g., glycol ethers (e.g., ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, 2-butoxyethanol, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, 2-phenoxyethanol, or those glycol ethers available under the trade designation “DOWANOL” from Dow Chemical Co., Midland, MI)); propylene carbonate; dibasic esters; and combinations thereof. In some embodiments, the solvent comprises at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a dibasic ester. In some embodiments, the solvent does not comprise or comprises less than 1% of a monohydric alcohol having 1 to 8 or more carbon atoms, a monohydric alcohol having 1 to 4 carbon atoms, or isopropanol.

[0069] In some embodiments, the solvent comprises at least one of a polyol or polyol ether independently having 2 to 10 (in some embodiments, 2 to 9 or 2 to 8) carbon atoms. In some embodiments, the solvent comprises a polyol. The term “polyol” refers to an organic molecule consisting of C, H, and O atoms connected to one another by C-H, C-C, C-O, O-H single bonds and having at least two C-O-H groups. In some embodiments, useful polyols have 2 to 10, 2 to 8, or 2 to 6 carbon atoms. In some embodiments, the solvent comprises a polyol ether. The term “polyol ether” refers to an organic molecule consisting of C, H, and O atoms connected to one another by C-H, C-C, C-O, O-H single bonds or C=C double bonds and which organic molecule is derivable, at least in theory, by at least partial etherification of a polyol. In some embodiments, the polyol ether has at least one C-O-H group and at least one C-O-C bond. In some embodiments, the polyol ether has at least two C-O-C bonds. Similarly, the term “polyol ether ester” refers to an organic molecule consisting of C, H, and O atoms connected to one another by C-H, C-C, C-O, O-H single bonds and C=C double bonds and which organic molecule is derivable, at least in theory, by at least partial etherification and esterification of a polyol. In some embodiments, the polyol ether ester has at least one C-O-C(O)-C group and at least one C-O-C bond. Useful polyol ethers and / or polyol ether esters can have 3 to 10, 3 to 8, or 5 to 8 carbon atoms. In some embodiments, the solvent comprises at least one of propylene carbonate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, 2-phenoxyethanol, a dibasic ester, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, or dipropylene glycol monomethyl ether.

[0070] In some embodiments, the solvent comprises at least 2, 2.5, 3, 4, or 5 weight percent of the groundstock composition. In some embodiments, the solvent comprises no more than 25, 20, 15, 12.5, or 10 weight percent of the groundstock composition.

[0071] In some embodiments, the make compositions of the present disclosure and / or make compositions useful in the adhesive systems of the present disclosure comprise a humidity stabilizer, which can also be referred to as a water scavenger. Examples of suitable humidity stabilizers include silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethyl-methyldimethoxysilane, O-methylcarbamatomethyl-trimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, O-ethyl-carbamatomethyl-triethoxysilane, 3-methacryloxypropyl-trimethoxysilane, methacryloxy-methyl-trimethoxysilane, methacryloxy-methyl-methyldimethoxysilane, methacryloxy-methyl-triethoxysilane, methacryloxy-methyl-methyldiethoxysilane, 3-acryloxypropyl-trimethoxysilane, acryloxy-methyl-trimethoxysilane, acryloxy-methyl-methyldimethoxysilane, acryloylmethyl-triethoxysilane, acryloxy-methyl-methyldiethoxysilane, the usual alkylalkoxysilanes, 3-glycidyloxypropyltrimethoxysilane, further functionalized organosilanes, and aminosilanes, which are also described below as adhesion promoters. In some embodiments, the make composition comprises at least 0.01 wt%, in some embodiments at least 0.03 wt% and not more than 5 wt%, 2 wt%, or 1 wt% of one or more humidity stabilizers.

[0072] In some embodiments, the make compositions of the present disclosure and / or make compositions useful in the adhesive systems of the present disclosure comprise an adhesion promoter. Useful adhesion promoters include those available under the trade designations "A1120", "A187", and "A189" from OSI and under the trade designation "Z9020" from Dow Chemical Company. Aminosilanes can be used as adhesion promoters. Examples of aminosilanes useful as adhesion promoters include gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltriisopropoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-(2-aminoethyl)aminopropyltrimethoxysilane, gamma-(2-aminoethyl)aminopropylmethyldimethoxysilane, gamma-(2-aminoethyl)aminopropyltriethoxysilane, gamma-(2-aminoethyl)aminopropylmethyldiethoxysilane, gamma-(2-aminoethyl)aminopropyltriisopropoxysilane, gamma-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-gamma-aminopropyltrimethoxysilane, N-vinylbenzyl-gamma-aminopropyltriethoxysilane, [Nu],[Nu]'-bis[3-trimethoxysilyl]propyl]ethylenediamine, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, and N-phenylaminomethyltrimethoxysilane. Suitable adhesion promoters also include titanates. In some embodiments, the make composition further comprises a titanate chelate. Examples of suitable titanate chelates include acetylacetonate titanate chelate, triethanolamine titanate chelate, and those available under the trade designation "TYZOR" from Dorfketal, Germany. In some embodiments, the make composition comprises at least 0.01 wt%, in some embodiments at least 0.1 wt%, or at least 0.5 wt% of the adhesion promoter(s). In some embodiments, the make composition comprises no more than 5 wt%, in some embodiments no more than 2 wt% of the adhesion promoter(s).

[0073] In some embodiments, the make compositions of the present disclosure and / or that can be used in the adhesive systems of the present disclosure comprise a wetting agent. Useful wetting agents include surfactants. Surfactants are compounds that lower the surface tension when dissolved in water or aqueous solutions, or lower the interfacial tension between two liquids or between a liquid and a solid. Surfactants useful in the practice of the present disclosure include cationic, anionic, zwitterionic, or non-ionic surfactants. Examples of anionic surfactants include sulfonates, carboxylates, and phosphates. Examples of cationic surfactants include quaternary ammoniums. Examples of non-ionic surfactants include block copolymers containing ethylene oxide and silicone surfactants such as ethoxylated alcohols, ethoxylated fatty acids, sorbitan derivatives, lanolin derivatives, ethoxylated nonylphenols, and alkoxylated polysiloxanes. In some embodiments, the make composition comprises at least 0.1 wt%, in some embodiments at least 0.5 wt% of one or more wetting agents. In some embodiments, the make composition comprises no more than 5 wt%, in some embodiments no more than 2 wt% of one or more wetting agents.

[0074] In some embodiments, the make compositions of the present disclosure and / or that can be used in the adhesive systems of the present disclosure comprise a pH adjusting agent. In some embodiments, it can be useful to adjust the pH of the aqueous phase to a range of 8 to 12 or 8 to 10. Examples of useful pH adjusting bases include Bronsted bases such as sodium hydroxide or ammonium hydroxide, organic bases such as triethylamine, and combinations thereof. In some embodiments, it can be useful to adjust the pH of the aqueous phase to a range of 2 to 6 range or 3 to 5 range. Examples of useful pH adjusting acids include Bronsted acids such as hydrochloric acid, organic acids such as acetic acid, and combinations thereof.

[0075] The present disclosure provides an adhesive system comprising a primer composition described above in any of the embodiments of the primer composition in combination with an adhesive tape. In some embodiments, the primer composition can be used to improve the adhesion of the adhesive tape to a first substrate (e.g., a first substrate to be joined with a second substrate). In some embodiments, the primer composition is not a component of the adhesive tape. For example, the primer composition is not disposed on the tape backing to improve adhesion between the adhesive and the backing. In some embodiments, the primer composition comprises a polymer and a solvent dispersed in water, wherein the water comprises at least 50 wt% of the primer composition. In some embodiments, the primer composition comprises at least one of a polyamide, a polyurethane, or a polyacrylate, each of which can be as described above in any of the embodiments thereof. Advantageously, no heat or radiation and reactive chemicals are required in the primer or adhesive tape to provide beneficial adhesive properties in the adhesive system of the present disclosure. The adhesive tape generally adheres to the primed substrate surface without forming covalent bonds. For example, the adhesive tape generally does not react with the primer composition to form covalent bonds. The adhesive system can be used, for example, to bond substrates.

[0076] For the adhesive system, any suitable adhesive tape can be used, and the primer composition can be used to improve the adhesion of a variety of adhesives to a substrate. The adhesive on the adhesive tape can be in the form of a film or a foam. In some embodiments, the adhesive is a single layer. In other embodiments, the adhesive tape includes a multi-layer adhesive construction, such as a double-sided adhesive tape. For example, the multi-layer adhesive tape can have a first adhesive skin layer, a second adhesive skin layer, and a core layer positioned between the first adhesive skin layer and the second adhesive skin layer. The core layer is typically a foam backing layer and can be an adhesive or non-adhesive foam. In another example, the multi-layer adhesive tape can have a first adhesive layer, a film backing, and a second adhesive layer. The film backing can be an adhesive or non-adhesive layer.

[0077] In some embodiments, the adhesive tape useful in the adhesive systems of the present disclosure comprises a (meth)acrylate copolymer-based pressure sensitive adhesive. The (meth)acrylate copolymer has a glass transition temperature (Tg) that is typically no greater than 20°C, no greater than 10°C, no greater than 0°C, no greater than -10°C, no greater than -20°C, no greater than -30°C, no greater than -40°C, or no greater than -50°C. The glass transition temperature can be measured using techniques such as differential scanning calorimetry and dynamic mechanical analysis. Alternatively, the glass transition temperature can be estimated based on the monomers used to form the adhesive using the Fox equation. Lists of glass transition temperatures of homopolymers are available from a number of monomer suppliers such as BASF Corporation, Houston, TX, USA, Polyscience, Inc., Warrington, PA, USA, and Aldrich, St. Louis, MO, USA, as well as in various publications, for example, Mattioni et al., J. Chem. Inf. Comput. Sci., 2002, 42, 232-240, and many of the polymer property databases found at polymerdatabase.com.

[0078] The (meth)acrylate copolymer is typically formed from a monomer composition comprising at least one low Tg monomer. As used herein, the term "low Tg monomer" refers to a monomer that has a Tg of no greater than 20°C when homopolymerized (i.e., the Tg of a homopolymer formed from the low Tg monomer is no greater than 20°C). Suitable low Tg monomers are often selected from alkyl (meth)acrylates, heteroalkyl (meth)acrylates, aryl-substituted alkyl acrylates, and aryloxy-substituted alkyl acrylates. Examples of low Tg alkyl (meth)acrylate monomers are typically non-tertiary alkyl acrylates, but can be alkyl methacrylates having a linear alkyl group of at least 4 carbon atoms. Examples of alkyl (meth)acrylates include n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, sec-butyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-octyl acrylate, isooctyl acrylate, isononyl acrylate, isoamyl acrylate, n-decyl acrylate, isodecyl acrylate, n-decyl methacrylate, lauryl acrylate, isotridecyl acrylate, n-stearyl acrylate, isostearyl acrylate, and n-dodecyl acrylate. Isomers and mixtures of isomers of these monomers can be used.

[0079] Examples of low Tg (meth)acrylic heteroalkyl ester monomers tend to have at least 3 carbon atoms, at least 4 carbon atoms, or at least 6 carbon atoms, and can have up to 30 or more carbon atoms, up to 20 carbon atoms, up to 18 carbon atoms, up to 16 carbon atoms, up to 12 carbon atoms, or up to 10 carbon atoms. Specific examples of (meth)acrylic heteroalkyl esters include 2-ethoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, (meth)acrylic acid 2-methoxyethyl ester, and (meth)acrylic acid tetrahydrofurfuryl ester.

[0080] Examples of low Tg aryl-substituted alkyl acrylate or aryloxy-substituted alkyl acrylate include 2-biphenylhexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, and 2-phenethyl acrylate.

[0081] Some monomer compositions of the (meth)acrylic ester copolymer can include an optional polar monomer. Polar monomers have an ethylenically unsaturated group and a polar group, such as an acidic group or salts thereof, a hydroxyl group, a primary amido group, a secondary amido group, a tertiary amido group, or an amino group. Having a polar monomer is generally beneficial for pressure sensitive adhesive adhesion to a variety of substrates. Examples of polar monomers having an acidic group include ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Examples of such compounds include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, (meth)acrylic acid 2-carboxyethyl ester, methacrylic acid 2-sulfoethyl ester, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl phosphonic acid, and mixtures thereof. Due to their availability, the acid monomers are typically acrylic acid or methacrylic acid. - carboxyethyl ester, methacrylic acid 2-sulfoethyl ester, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl phosphonic acid, and mixtures thereof. Due to their availability, the acid monomers are typically acrylic acid or methacrylic acid.

[0082] Examples of polar monomers having a hydroxyl group include: (meth)acrylic acid hydroxyalkyl esters (e.g., (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 3-hydroxypropyl ester, and (meth)acrylic acid 4-hydroxybutyl ester), hydroxyalkyl (meth)acrylamides (e.g., 2-hydroxyethyl (meth)acrylamide or 3-hydroxypropyl (meth)acrylamide), ethoxylated (meth)acrylic acid hydroxyethyl ester (e.g., monomers commercially available under the trade designations CD570, CD571, and CD572 from Sartomer (Exton, PA, USA)), and aryloxy-substituted (meth)acrylic acid hydroxyalkyl esters (e.g., (meth)acrylic acid 2-hydroxy-2-phenoxypropyl ester).

[0083] Examples of polar monomers having a primary amide group include (meth)acrylamide. Examples of polar monomers having a secondary amide group include N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-t-octyl (meth)acrylamide, or N-octyl (meth)acrylamide.

[0084] Examples of polar monomers having a tertiary amide group include N-vinyl caprolactam, N-vinyl-2-pyrrolidone, (meth)acryloyl morpholine, and N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, and N,N-dibutyl (meth)acrylamide.

[0085] Polar monomers having an amino group include various N,N-dialkylaminoalkyl (meth)acrylates and N,N-dialkylaminoalkyl (meth)acrylamides. Examples include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylamide.

[0086] The monomer composition of the (meth)acrylate copolymer can optionally include a high Tg monomer. As used herein, the term "high Tg monomer" refers to a monomer that has a Tg, when homopolymerized, of greater than 30°C, greater than 40°C, or greater than 50°C (i.e., a homopolymer formed from the monomer has a Tg of greater than 30°C, greater than 40°C, or greater than 50°C). Some suitable high Tg monomers include (meth)acrylic acid, (meth)acrylate esters, and styrenic monomers. gMonomers having a single (meth)acryloyl group such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, (meth)acrylate ester, cyclohexyl methacrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, phenyl acrylate, benzyl methacrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 2-phenoxyethyl methacrylate, N-octyl (meth)acrylamide, and mixtures thereof. Other suitable high Tg monomers have a single vinyl group that is not a (meth)acryloyl group such as, for example, various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrenes (e.g., a-methyl styrene), vinyl halides, and mixtures thereof. Vinyl monomers having the group characteristic of polar monomers are considered polar monomers herein.

[0087] Generally, the pressure sensitive adhesive can comprise up to 100 weight % (e.g., 100 weight %) of low Tg monomer units. The weight % values are based on the total weight of monomer units in the polymeric material. In some embodiments, the (meth)acrylate polymer contains 40 weight % to 100 weight % of low Tg monomer units, 0 weight % to 15 weight % of polar monomer units, 0 weight % to 50 weight % of high Tg monomer units, and 0 weight % to 15 weight % of vinyl monomer units. In some embodiments, the (meth)acrylate polymer comprises 60 weight % to 100 weight % of low Tg monomer units, 0 weight % to 10 weight % of polar monomer units, 0 weight % to 40 weight % of high Tg monomer units, and 0 weight % to 10 weight % of vinyl monomer units. In some embodiments, the (meth)acrylate polymer comprises 75 weight % to 100 weight % of low Tg monomer units, 0 weight % to 10 weight % of polar monomer units, 0 weight % to 25 weight % of high Tg monomer units, and 0 weight % to 5 weight % of vinyl monomer units.

[0088] In some embodiments, the adhesive tapes useful in the adhesive systems of the present disclosure comprise adhesives (in some embodiments, pressure sensitive adhesives) based on semi-crystalline polymer resins such as polyolefins and polyolefin copolymers (e.g., polymer resins based on monomers having between 2 and 8 carbon atoms such as low density polyethylene, high density polyethylene, polypropylene, and ethylene-propylene copolymers); polyesters and copolyesters; polyamides and copolyamides; fluorinated homopolymers and copolymers; polyalkylene oxides (e.g., polyethylene oxide and polypropylene oxide); polyvinyl alcohol; ionomers (e.g., ethylene-methacrylic acid copolymers neutralized with a base); and cellulose acetate. Additional examples of polymers useful in the adhesives in the adhesive tapes include amorphous polymers such as polyacrylonitrile polyvinyl chloride, thermoplastic polyurethane, aromatic epoxide, polycarbonate, amorphous polyester, amorphous polyamide, ABS block copolymer, polyphenylene ether alloy, ionomer (e.g., ethylene-methacrylic acid copolymer neutralized to a salt), fluorinated elastomer, and polydimethylsiloxane.

[0089] In some embodiments, the adhesive tapes useful in the adhesive systems of the present disclosure comprise adhesives (in some embodiments, pressure sensitive adhesives) based on elastomers such as polybutadiene, polyisoprene, polychloroprene, random and block copolymers of styrene and dienes (e.g., SBR), and ethylene-propylene-diene monomer rubbers. Such polymers are often combined with tackifying resins. Block copolymer adhesive compositions can comprise a first block copolymer comprising at least one rubbery block comprising a first polymeric conjugated diene, a hydrogenated derivative thereof, or a combination thereof, and at least one glassy block comprising a first polymeric monovinyl aromatic monomer. In some embodiments, the first block copolymer is of the formula Q n- multi-arm block copolymers of Y, wherein Q represents an arm of the multi-arm block copolymer; n represents the number of arms and is an integer of at least 3; and Y is a residue of a multifunctional coupling agent. Each arm Q independently has the formula R-G, wherein R represents a rubbery block and G represents a glassy block. In some embodiments, the first block copolymer is a multi-modal asymmetric star block copolymer. In some embodiments, the adhesive further comprises a second block copolymer. The second block copolymer comprises at least one rubbery block and at least one glassy block. The rubbery block comprises a polymerized second conjugated diene, a hydrogenated derivative thereof, or a combination thereof, and the glassy block comprises a second polymerized monovinyl aromatic monomer. In some embodiments, the second block copolymer is a linear block copolymer. In some embodiments, the pressure sensitive adhesive based on a block copolymer further comprises a first high Tg tackifier having a Tg of at least 60 °C, wherein the first high Tg tackifier is compatible with the at least one rubbery block. In some embodiments, the block copolymer adhesive composition further comprises a second high Tg tackifier having a Tg of at least 60 °C, wherein the second high Tg tackifier is compatible with the at least one glassy block.

[0090] In some embodiments, the elastomer-based adhesive is as described, for example, in U.S. 9,556,367 (Waid et al.). The adhesive is a pressure sensitive adhesive and comprises 92 to 99.9 parts of the block copolymer adhesive composition and 0.1 to less than 10 parts of an acrylic adhesive composition. The acrylic adhesive composition comprises 70 parts to 100 parts of an acrylate or methacrylate ester of at least one non-tertiary alkyl alcohol, wherein the non-tertiary alkyl alcohol comprises 4 to 20 carbon atoms; and 0 parts to 30 parts of a copolymerized reinforcing monomer.

[0091] In some embodiments, the adhesive tapes useful in the adhesive systems of the present disclosure comprise adhesives based on pressure sensitive adhesives and hot melt applied adhesives comprising polymers prepared from non-photopolymerizable monomers. Such polymers can be adhesive polymers (i.e., polymers that are inherently adhesive) or polymers that are not inherently adhesive but can form an adhesive composition when compounded with components such as plasticizers and / or tackifiers. Specific examples include poly-alpha-olefins (e.g., polyoctenes, polyhexenes, and atactic polypropylenes), block copolymer based adhesives, natural and synthetic rubbers, silicone adhesives, ethylene-vinyl acetate, and epoxy-containing structural adhesive blends (e.g., epoxy-acrylate and epoxy-polyester blends).

[0092] The adhesive in the adhesive tape useful in the adhesive system of the present disclosure can optionally contain other components such as fillers, antioxidants, viscosity modifiers, pigments (e.g., carbon black, titanium dioxide, or any other suitable pigment), tackifying resins, and fibers. These components can be added to the adhesive to the extent that they do not alter the desired properties of the final product.

[0093] A variety of commercially available adhesive tapes are useful in the adhesive system of the present disclosure. For example, the adhesive system can include adhesive tapes available under the trade designation "VHB" from 3M Company, St. Paul, MN. These include the "3M VHB TAPE LSE" series, the "3M VHB TAPE GPH" series, "3M VHB TAPE 4941," and "3M VHB TAPE 4611."

[0094] In some embodiments, the adhesive tape useful in the adhesive system of the present disclosure comprises a semi-structural adhesive. The semi-structural adhesive has a shear storage modulus of at least or greater than 0.5 megapascals (MPa) as measured on a rheometer at 25°C when applying an oscillatory strain of 1 hertz (Hz) within the linear viscoelastic region of the adhesive film. In some embodiments, the adhesive has a storage modulus of at least 1 MPa or 1.5 MPa. In some embodiments, the adhesive film of the present disclosure has a storage modulus of at most 4 MPa, 3.5 MPa, 3 MPa, 2.5 MPa, or 2 MPa. The storage modulus of the bulk adhesive film can be conveniently measured as described in the Examples below. In embodiments where the adhesive film is a multi-layer film, the storage modulus can be determined by atomic force microscopy (AFM)-based nanoindentation at frequencies and temperatures within the rheology-relevant regime (0.1 Hz to 100 Hz) as described in more detail below.

[0095] Semi-structural adhesives exceed the Dahlquist criteria, but provide excellent wet-out adhesion to substrates in the adhesive system of the present disclosure. As shown in the Examples below, semi-structural adhesives can provide lap shear strength values of 2.5 MPa to 3.5 MPa. Thus, the adhesive film of the present disclosure has excellent cohesive strength and can provide lap shear adhesion values much higher than typical PSAs.

[0096] In some embodiments, the semi-structural adhesive in the adhesive system of the present disclosure comprises a first (meth)acrylate copolymer comprising at least 55 wt% of linear or branched (meth)acrylic alkyl ester monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the first (meth)acrylate copolymer comprises at least 60%, 65 wt%, or 70 wt% of linear or branched (meth)acrylic alkyl ester monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the first (meth)acrylate copolymer comprises less than 85 wt% or at most 84 wt%, 83 wt%, 82 wt%, 81 wt%, or 80 wt% of linear or branched (meth)acrylic alkyl ester monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the semi-structural adhesive in the adhesive system of the present disclosure comprises a second (meth)acrylate copolymer comprising at least 55 wt%, 60 wt%, 65 wt%, or 70 wt% of linear or branched (meth)acrylic alkyl ester monomer units, based on the weight of the second (meth)acrylate copolymer. In some embodiments, the second (meth)acrylate copolymer comprises less than 85 wt% or at most 84 wt%, 83 wt%, 82 wt%, 81 wt%, or 80 wt% of linear or branched (meth)acrylic alkyl ester monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the linear or branched (meth)acrylic alkyl ester monomer units are C1-C 32 (meth)acrylic alkyl ester monomer units, C1-C 24 (meth)acrylic alkyl ester monomer units, or C1-C 18 (meth)acrylic alkyl ester monomer units.

[0097] Examples of suitable (meth)acrylic alkyl esters include those represented by the formula CH2=C(R)COOR’, wherein R is hydrogen or a methyl group, and R’ is an alkyl group having 1 to 30, 4 to 30, 6 to 30, 8 to 30, 6 to 24, 6 to 20, 6 to 18, 8 to 24, 8 to 20, or 8 to 20 carbon atoms, and can be linear or branched. Examples of suitable monomers represented by this formula include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-octyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl acrylate, undecyl (meth)acrylate, n-dodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, cetyl (meth)acrylate, 2-propylheptyl (meth)acrylate, stearyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate. Suitable monomer units further include mixtures of at least two or at least three structural isomers of a (meth)acrylic secondary alkyl ester represented by formula III as described above in any of its embodiments. In some embodiments, the first (meth)acrylic ester copolymer and / or the optional second (meth)acrylic ester copolymer comprises at least one of 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isooctyl (meth)acrylate. In some embodiments, the first (meth)acrylic ester copolymer and / or the second (meth)acrylic ester copolymer comprises 2-ethylhexyl (meth)acrylate.

[0098] The first (meth)acrylate copolymer of the semi-structural adhesive useful in the adhesive systems of the present disclosure comprises 15 to 40 weight percent of (meth)acrylic monomer units. In some embodiments, the first (meth)acrylate copolymer comprises at least 15 weight percent, greater than 15 weight percent, at least 16 weight percent, or at least 17 weight percent of (meth)acrylic monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the second (meth)acrylate copolymer, when present in the semi-structural adhesive, comprises greater than 15 to 40 weight percent of (meth)acrylic monomer units. In some embodiments, the second (meth)acrylate copolymer comprises greater than 15 weight percent, at least 16 weight percent, or at least 17 weight percent of (meth)acrylic monomer units, based on the weight of the second (meth)acrylate copolymer. In some embodiments, the first (meth)acrylate copolymer in the semi-structural adhesive comprises 15.5 to 40 weight percent, 16 to 40 weight percent, 16 to 35 weight percent, 16 to 30 weight percent, 16 to 25 weight percent, 17 to 25 weight percent, 17 to 23 weight percent, 17 to 20 weight percent, or 17 to 19.5 weight percent of (meth)acrylic monomer units, based on the weight of the first (meth)acrylate copolymer. In some embodiments, the optional second (meth)acrylate copolymer in the semi-structural adhesive comprises 15.5 to 40 weight percent, 16 to 40 weight percent, 16 to 35 weight percent, 16 to 30 weight percent, 16 to 25 weight percent, 17 to 25 weight percent, 17 to 23 weight percent, or 17 to 20 weight percent of (meth)acrylic monomer units, based on the weight of the second (meth)acrylate copolymer. Examples of (meth)acrylic monomer units include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, ethyl acrylate, crotonic acid, citraconic acid, cinnamic acid, beta-carboxyethyl acrylate, and 2-methacryloyloxyethyl succinate. In some embodiments, the (meth)acrylic monomer units are acrylic monomer units or methacrylic monomer units. The (meth)acrylic monomer units include salts of these acids, such as alkali metal salts and ammonium salts.

[0099] In some embodiments, the first (meth)acrylate copolymer of the semi-structural adhesive useful in the adhesive systems of the present disclosure further comprises monomer units of "high T g " monomers, which high T g monomers, when polymerized, provide a homopolymer (i.e., a homopolymer formed from the monomer) having a glass transition temperature (T g ) of at least 50 °C, 60 °C, or 70 °C. gat least 50°C, 60°C, or 70°C). In embodiments in which the first (meth)acrylate copolymer has 15 weight percent of (meth)acrylic monomer units based on the weight of the first (meth)acrylate copolymer, the first (meth)acrylate copolymer typically also includes at least 5 weight percent (in some embodiments, at least 7.5 weight percent, 10 weight percent, 12.5 weight percent, or 15 weight percent) of monomer units of a "high T g " monomer. The T g of a homopolymer is measured by differential scanning calorimetry and is reported in the "Polymer Property Database" found at polymerdatabase.com. Some suitable high T g monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl (meth)acrylate, cyclohexyl methacrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, phenyl acrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl (meth)acrylate, t-butylcyclohexyl methacrylate, 2-phenoxyethyl methacrylate, N-octyl (meth)acrylamide, tetrahydrofurfuryl methacrylate, and mixtures thereof. Other suitable high T g monomers have a single vinyl group that is not a (meth)acryloyl group, such as various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrenes (e.g., a-methyl styrene), vinyl halides, and mixtures thereof. In some embodiments, the optional second (meth)acrylate copolymer also includes monomer units of a high T g monomer, including any of the above monomer units in any of the above weight percentages.

[0100] The first (meth)acrylate copolymer of the semi-structural adhesive useful in the adhesive systems of the present disclosure comprises from 0.050 wt% to 5.0 wt% of monomeric units of a crosslinking monomer having more than one (meth)acrylate group, based on the weight of the (meth)acrylate copolymer. Suitable crosslinking monomers include diacrylates of diols, such as ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, butane-1,3-diyl diacrylate, pentanediol diacrylate, hexanediol diacrylate (including 1,6-hexanediol diacrylate), heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, decanediol diacrylate, and dimethacrylates of any of the foregoing diacrylates. Other suitable multifunctional monomers include polyacrylates of polyols, such as glyceryl triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol pentaacrylate, methacrylates of the foregoing acrylates, and combinations thereof. Other suitable multifunctional crosslinking monomers include divinyl benzene, allyl methacrylate, diallyl maleate, diallyl phthalate, and combinations thereof. Further suitable multifunctional crosslinking monomers include multifunctional acrylate oligomers comprising two or more acrylate groups. The multifunctional acrylate oligomers can be urethane acrylate oligomers, epoxy acrylate oligomers, polyester acrylates, polyether acrylates, polyacrylic acrylates, methacrylates of any of the foregoing acrylates, or combinations thereof. Combinations of any of these crosslinking monomers can be useful. In some embodiments, up to 4.0 wt%, 3.0 wt%, 2.0 wt%, or 1.0 wt% of the monomeric units in the first (meth)acrylate copolymer are derived from crosslinking monomers. In some embodiments, at least 0.10 wt%, 0.15 wt%, 0.20 wt%, 0.25 wt%, 0.30 wt%, 0.40 wt%, 0.50 wt%, 0.60 wt%, or 0.70 wt% of the monomeric units in the first (meth)acrylate copolymer are derived from crosslinking monomers. When present, the second (meth)acrylate copolymer can comprise any of these crosslinking monomeric units in any of these amounts, or can be free of crosslinking monomeric units.

[0101] The acrylate polymers can be analyzed by nuclear magnetic resonance spectroscopy (NMR) to identify the monomeric units in the polymer. Depending on the level of crosslinking in the polymer, either solid state or solution NMR can be useful. For solid state NMR, the acrylate polymer can be swelled in a suitable solvent for analysis. 1 H or 13 C NMR) to identify the monomeric units in the polymer. Depending on the level of crosslinking in the polymer, either solid state or solution NMR can be useful. For solid state NMR, the acrylate polymer can be swelled in a suitable solvent for analysis.

[0102] In some embodiments of the semi-structural adhesive in the adhesive system of the present disclosure, the Tg of the first (meth)acrylate copolymer and the second (meth)acrylate copolymer, when present, is each independently in the range of between 2 °C and 100 °C, between 2 °C and 80 °C, between 2 °C and 60 °C, between 2 °C and 50 °C, between 2 °C and 45 °C, between 5 °C and 45 °C, between 5 °C and 40 °C, between 5 °C and 35 °C, or between 10 °C and 30 °C. In some embodiments, the Tg of the first (meth)acrylate copolymer and the second (meth)acrylate copolymer, when present, is each independently not greater than 100 °C, not greater than 80 °C, not greater than 60 °C, not greater than 50 °C, not greater than 45 °C, or even not greater than 40 °C. g each independently in the range of between 2 °C and 100 °C, between 2 °C and 80 °C, between 2 °C and 60 °C, between 2 °C and 50 °C, between 2 °C and 45 °C, between 5 °C and 45 °C, between 5 °C and 40 °C, between 5 °C and 35 °C, or between 10 °C and 30 °C. In some embodiments, the Tg of the first (meth)acrylate copolymer and the second (meth)acrylate copolymer, when present, is each independently not greater than 100 °C, not greater than 80 °C, not greater than 60 °C, not greater than 50 °C, not greater than 45 °C, or even not greater than 40 °C. g each independently not greater than 100 °C, not greater than 80 °C, not greater than 60 °C, not greater than 50 °C, not greater than 45 °C, or even not greater than 40 °C.

[0103] In some embodiments, the semi-structural adhesive in the adhesive system of the present disclosure has a thickness of at least 0.3 millimeters. In some embodiments, the semi-structural adhesive has a thickness in the range of 300 micrometers to 6000 micrometers, 300 micrometers to 4000 micrometers, 300 micrometers to 2000 micrometers, 500 micrometers to 2000 micrometers, 800 micrometers to 1500 micrometers, or 600 micrometers to 1300 micrometers.

[0104] In some embodiments of the semi-structural adhesive tape in the adhesive system of the present disclosure, the semi-structural adhesive comprises 65 weight percent to 99 weight percent, 70 weight percent to 95 weight percent, 75 weight percent to 95 weight percent, 75 weight percent to 90 weight percent, or even 75 weight percent to 85 weight percent of the first (meth)acrylate copolymer, and wherein the weight percent is based on the total weight of the semi-structural adhesive. In some embodiments, the semi-structural adhesive comprises 1 weight percent to 35 weight percent, 1 weight percent to 30 weight percent, 2 weight percent to 25 weight percent, 3 weight percent to 25 weight percent, 3 weight percent to 20 weight percent, 4 weight percent to 20 weight percent, or even 4 weight percent to 15 weight percent of the second (meth)acrylate copolymer, and wherein the weight percent is based on the total weight of the semi-structural adhesive.

[0105] In some embodiments, the semi-structural adhesive in the adhesive system of the present disclosure comprises no more than 5, 4, 3, 2, 1, or 0 weight percent of an additional (meth)acrylate copolymer having from 0.1 to 15 weight percent (in some embodiments, from 0.1 to 12, from 0.1 to 11, from 0.1 to 10, from 0.2 to 10, from 0.2 to 9, from 0.2 to 8, from 0.3 to 8, from 0.5 to 8, from 0.5 to 6, from 1 to 6, or from 1 to 5 weight percent) of (meth)acrylic monomer units based on the weight of the additional (meth)acrylate copolymer. Such additional (meth)acrylate copolymers in the adhesive film of the present disclosure will tend to decrease the T g and / or storage modulus of the semi-structural adhesive, and will also tend to decrease the cohesive strength of the semi-structural adhesive.

[0106] The first (meth)acrylate copolymer and the second (meth)acrylate in some embodiments of the semi-structural adhesive useful in the adhesive system of the present disclosure, the (meth)acrylate copolymer of the pressure sensitive adhesive useful in the adhesive system of the present disclosure, and the polyacrylate useful in some embodiments of the make coat composition, can each be prepared by any conventional free radical polymerization process, including solution, radiation, bulk, dispersion, emulsion, solventless, and suspension processes. The resulting copolymers can be random or block copolymers. In some embodiments, the first (meth)acrylate copolymer is prepared as a solution or slurry copolymer composition.

[0107] A typical solution polymerization process is carried out by adding the monomers, a suitable solvent, and optionally a chain transfer agent to a reaction vessel; adding a free radical initiator; purging with nitrogen; and maintaining the reaction vessel at an elevated temperature, typically in the range of about 40°C to 100°C, until the reaction is complete, usually for about 1 hour to 24 hours, depending on batch size and temperature. Examples of solvents are methanol, tetrahydrofuran, ethanol, isopropanol, t-butanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and ethylene glycol alkyl ethers. These solvents can be used individually or as mixtures thereof. In a typical thermal polymerization process, the monomer mixture can be subjected to thermal energy in the presence of a thermal polymerization initiator, i.e., a thermal initiator. Examples of suitable thermal initiators are those available under the trade designation "VAZO" from DuPont.

[0108] Slurry polymer technology includes partially polymerizing monomers to produce a slurry polymer that contains (meth)acrylate copolymer and un-polymerized monomers. The slurry polymer composition is polymerized to a useable coating viscosity that makes it available to be coated onto a substrate (such as a backing) and further polymerized. In some embodiments, the polymerization is carried out in the absence of solvents such as ethyl acetate, toluene, or tetrahydrofuran, which do not react with the functional groups of the components of the slurry polymer.

[0109] In some embodiments, the coatable slurry polymer of the adhesive tape useful in the adhesive systems of the present disclosure is prepared by photoinitiated free radical polymerization. The polymerization to achieve a coatable viscosity can be carried out such that the conversion of monomers to polymer is at most about 10%. The polymerization can be achieved by exposing the slurry polymer composition to light energy in the presence of a photoinitiator. When the desired conversion and viscosity have been achieved, the polymerization can be terminated by removing the light source and by quenching the propagating radicals by bubbling air (oxygen) into the solution. In the case of using ionizing radiation to initiate the polymerization, for example, an energy-activated initiator can not be needed.

[0110] In some embodiments, the free radical photoinitiator that can be used to make the adhesive tape in the adhesive system of the present disclosure is a Type I (cleavage type) photoinitiator. Cleavage type photoinitiators include acetophenone, a-aminoalkyl phenone, benzoin ether, benzoyl oxime, acyl (e.g., benzoyl) phosphine oxide, acyl (e.g., benzoyl) phosphinic ester, and mixtures thereof. Examples of useful benzoin ethers include benzoin methyl ether and benzoin butyl ether. Examples of suitable acetophenone compounds include 4-diethylaminobenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2 dimethylamino-4'-morpholinobutyrophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxyacetophenone, and 2,2-dimethoxy-1,2-diphenylethan-1-one. Examples of suitable acyl phosphine oxide, acyl phosphinic ester, and acyl phosphonate compounds include bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinic ester, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, dimethyl pivaloyl phosphonate, and poly(oxy-1,2-ethanediyl), a,a',a''-1,2,3-propanetriyl tris[ω-[[phenyl(2,4,6-trimethylbenzoyl) phosphinyl]oxy]. Additional suitable photoinitiators include substituted a-ketols such as 2-methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalene-sulfonyl chloride; and photosensitive oximes such as 1-phenyl-1,2-propanedione-2-(O-ethoxy-carbonyl)oxime. Many photoinitiators are available, for example, under the trade designation "IRGACURE" from BASF, Vandalia, Ill., under the trade designation "OMNIRAD" and "ESACURE" from IGM Resins, Waalwijk, Netherlands. Two or more of any of these photoinitiators can also be used together in any combination. Additional photoinitiators can be added to the mixture to be coated after the copolymer has been formed (i.e., the photoinitiator can be added to the slurry polymer mixture).

[0111] The degree of conversion (monomer to copolymer) can be monitored during irradiation by measuring the refractive index of the polymerization mixture.

[0112] If desired, a chain transfer agent can be added to the monomer mixture to make any of the acrylic copolymers disclosed herein (e.g., the polyacrylate in the primer, the pressure sensitive adhesive in the adhesive tape, and the semi-structural adhesive in the adhesive tape). Examples of chain transfer agents include carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. In some embodiments, the chain transfer agent comprises at least one of isooctyl mercaptoacetate or carbon tetrabromide.

[0113] The adhesive (e.g., pressure sensitive adhesive or semi-structural adhesive) in the adhesive tape of the adhesive system of the present disclosure can include tackifying resins, particularly hydrogenated hydrocarbon tackifiers, as optional ingredients. Examples of hydrogenated hydrocarbon tackifiers include C9 and C5 hydrogenated hydrocarbon tackifiers. Examples of C9 hydrogenated hydrocarbon tackifiers include those sold under the trade designations "REGALITE S-5100," "REGALITE R-7100," "REGALITE R-9100," "REGALITE R-1125," "REGALITE S-7125," "REGALITE S-1100," "REGALITE R-1090," "REGALREZ 6108," "REGALREZ 1085," "REGALREZ 1094," "REGALREZ 1126," "REGALREZ 1139," and "REGALREZ 3103" sold by Eastman Chemical Co., Middelburg, Netherlands; "PICCOTAC" and "EASTOTAC" sold by Eastman Chemical Co.; "ARKON P-140," "ARKON P-125," "ARKON P-l 15," "ARKON P-100," "ARKON P-90," "ARKON M-135," "ARKON M-l 15," "ARKON M-100," and "ARKON M-90" sold by Arakawa Chemical Inc. (Chicago, IL); and "ESCOREZ 5000 series" sold by Exxon Mobil Corp., Irving, TX. In some embodiments, the tackifier is a partially hydrogenated C9 hydrogenated tackifier, a fully hydrogenated C9 hydrogenated tackifier, or a combination thereof. In some embodiments, the adhesive useful in the adhesive system of the present disclosure is substantially free of tackifying resins, particularly free of hydrocarbon tackifying resins.

[0114] If desired, other additives can be added to the adhesive tape of the adhesive system of the present disclosure (e.g., to the pressure sensitive adhesive or semi-structural adhesive). For example, leveling agents, ultraviolet absorbers, hindered amine light stabilizers (HALS), oxygen inhibitors, wetting agents, rheology modifiers, defoamers, biocides, flame retardants, and dyes can be included. All of these additives and their uses are known to those skilled in the art and can be used so long as they do not deleteriously affect the adhesive properties.

[0115] In some advantageous aspects, the adhesive (e.g., semi-structural adhesive or pressure sensitive adhesive) of the adhesive tape useful in the adhesive system of the present disclosure comprises a filler material, specifically, a particulate filler material. In some embodiments, the optional filler material for use herein includes at least one of polymeric microspheres, hollow ceramic microspheres, or glass bubbles.

[0116] In some embodiments, the adhesive (e.g., semi-structural adhesive or pressure sensitive adhesive) of the adhesive tape useful in the adhesive system of the present disclosure takes the form of a foam. The foam includes voids, which can be open or closed. In some embodiments, the voids are present in the foam in an amount of at least 5 vol%, 10 vol% to 55 vol%, 10 vol% to 45 vol%, 15 vol% to 45 vol%, or 20 vol% to 45 vol%. The density of the adhesive film in the form of a foam is typically in the range of 0.45 g / cm3to 1.5 g / cm3, 0.45 g / cm3to 1.10 g / cm3, 0.50 g / cm3to 1.00 g / cm3, 0.60 g / cm3to 0.95 g / cm3, 0.70 g / cm3to 0.95 g / cm3, or 0.80 g / cm3to 0.90 g / cm3. 3 to 1.5 g / cm3, 3 0.45 g / cm3 3 to 1.10 g / cm3 3 0.50 g / cm3 3 to 0.95 g / cm3 3 0.60 g / cm3 3 to 0.95 g / cm3 3 0.70 g / cm3 3 to 0.95 g / cm3 3 .

[0117] In some embodiments, the thickness of the adhesive foam of the adhesive tape useful in the adhesive system of the present disclosure is in the range of 100 micrometers to 6000 micrometers, 200 micrometers to 4000 micrometers, 500 micrometers to 2000 micrometers, or 800 micrometers to 1500 micrometers. In some embodiments, the thickness of the adhesive foam is at least 300 micrometers. It will be apparent to those skilled in the art, in light of this specification, that the thickness of the foamed adhesive will depend on the intended application.

[0118] Void spaces or cells in the foam can be produced in any known manner described in the art, and include the use of a gas or blowing agent and / or the inclusion of hollow particles into the composition used for the foam. For example, according to one method of producing a foam described in US 4,415,615 (Esmay et al.), an acrylic foam can be obtained by frothing a composition containing acrylic ester monomers and optional comonomers, coating the frothed foam on a backing, and polymerizing the frothed composition. It is also possible to coat the non-frothed composition of acrylic ester monomers and optional comonomers to a backing and then simultaneously froth and polymerize the composition. Frothing of the composition can be achieved by stirring a gas into the polymerizable composition, optionally in the presence of a surfactant (e.g., a hydrocarbon or fluorine-containing compound surfactant) or surface-modified nanoparticles to stabilize the foam. Inert gases such as nitrogen, argon, and carbon dioxide can be useful, particularly where the polymerization is photo-initiated.

[0119] In some embodiments, the adhesive foam of the adhesive tape useful in the adhesive systems of the present disclosure incorporates hollow fillers, such as hollow polymeric particles, hollow glass microspheres, and hollow ceramic microspheres. Hollow polymeric microspheres include elastomeric particles available, for example, under the trade designation “EXPANCEL” from Akzo Nobel, Amsterdam, The Netherlands. Examples of hollow ceramic microspheres include alumina / silica microspheres having a particle size in the range of 5 micrometers to 300 micrometers and a specific gravity of 0.7 (“FILLITE,” Pluress-Stauffer International), aluminum silicate microspheres having a specific gravity of about 0.45 to about 0.7 (“Z-LIGHT”), calcium carbonate-coated polyvinylidene copolymer microspheres having a specific gravity of 0.13 (“DUALITE 6001AE,” Pierce & Stevens Corp.), and glass bubbles sold by 3M Company, Saint Paul, Minnesota, under the trade designation “3M GLASS BUBBLES” in grades K1, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65, and “3M GLASS BUBBLES” of any HGS series. Foams containing hollow microspheres are referred to as syntactic foams. The foamed adhesive can also include a hydrocarbon elastomer as described in U.S. Patent No. 5,024,880 (Vesley et al.).

[0120] The adhesive of the adhesive tape useful in the adhesive system of the present disclosure can be prepared by simply blending the (meth)acrylate copolymer, optionally with optional ingredients such as filler materials and tackifying resins. The copolymer can be blended using several conventional methods such as melt blending, solvent blending, or any suitable physical means.

[0121] Physical mixing devices that provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be used to prepare the uniform blend. Both batch and continuous physical blending methods can be used. Examples of batch methods include BRABENDER (e.g., BRABENDER PREP CENTER available from C.W. Brabender Instruments, Inc.; South Hackensack, NJ) or BANBURY internal mixing and roll milling (using equipment available from FARREL COMPANY, Ansonia, CT). Examples of continuous methods include single screw extrusion, twin screw extrusion, round

[0122] In some embodiments, the semi-structural adhesive of the adhesive tape useful in the adhesive systems of the present disclosure comprises 65 to 98 weight percent, 70 to 95 weight percent, 75 to 95 weight percent, 75 to 90 weight percent, or 75 to 85 weight percent of the first (meth)acrylate copolymer; 0 to 35 weight percent, 1 to 35 weight percent, 1 to 30 weight percent, 2 to 25 weight percent, 3 to 25 weight percent, 3 to 20 weight percent, 4 to 20 weight percent, or 4 to 15 weight percent of the second (meth)acrylate copolymer; and, optionally, 2 to 15 weight percent, 2 to 14 weight percent, or 2 to 12 weight percent of a filler material comprising at least one of polymeric microspheres and glass bubbles, wherein the weight percent is based on the total weight of the semi-structural adhesive.

[0123] In some embodiments, the second (meth)acrylate copolymer of the semi-structural adhesive tape for use in the adhesive systems of the present disclosure is prepared using a substantially solvent-free free radical polymerization process, in particular a substantially solvent-free thermal free radical polymerization process. In some embodiments, the second (meth)acrylate copolymer for use herein is prepared by a substantially adiabatic polymerization process. Conversion (conversion of monomers to copolymer) degree can be monitored during polymerization by measuring the refractive index of the polymerization mixture.

[0124] In some embodiments, the second (meth)acrylate copolymer of the semi-structural adhesive tape for use in the adhesive systems of the present disclosure is obtained as a prepolymer composition having a polymer conversion of greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, or greater than 45%, in some embodiments having a polymer conversion comprised between 10% and 60%, between 20% and 55%, between 30% and 50%, or even between 35% and 50%.

[0125] According to one aspect of the present disclosure, the semi-structural adhesive useful in the adhesive tape of the adhesive system of the present disclosure can be prepared by incorporating a second (meth)acrylate copolymer into a curable precursor composition of a first (meth)acrylate copolymer comprising linear or branched alkyl (meth)acrylate monomers, (meth)acrylic monomers, crosslinking monomers, optionally a polymerization initiator, and optionally a particulate filler, thereby forming a curable precursor composition of an adhesive film. The first (meth)acrylate copolymer is then formed in situ in a second step and by polymerizing the linear or branched alkyl (meth)acrylate monomers, (meth)acrylic monomers, crosslinking monomers in the presence of the second (meth)acrylate copolymer to form the first (meth)acrylate copolymer. In some embodiments, the second (meth)acrylate copolymer is diluted into the curable precursor composition of the first (meth)acrylate copolymer and mixed by shaking. In some embodiments, the polymerization of the linear or branched alkyl (meth)acrylate monomers, (meth)acrylic monomers, crosslinking monomers in the presence of the second (meth)acrylate copolymer to form the first (meth)acrylate copolymer is carried out using actinic radiation.

[0126] According to another aspect, the adhesive useful in the adhesive tape of the adhesive system of the present disclosure is a multilayer adhesive assembly comprising an adhesive as described above in the form of a first adhesive layer (in some embodiments a first adhesive foam layer), which adhesive further comprises a second adhesive layer adjacent to the first adhesive film layer. The first adhesive layer and the second adhesive layer can be a pressure sensitive adhesive as described above, a semi-structural adhesive as described above, or a combination of both.

[0127] This type of multilayer adhesive assembly, and in particular a double layer or skin-core-skin foam tape assembly, is advantageous when compared to a single layer adhesive, because the adhesion (fast adhesion) can be adjusted by the formulation of the second adhesive layer (also often referred to as the skin layer), while other properties / requirements of the overall assembly such as application issues, distortion issues and energy distribution can be addressed by the appropriate formulation of the first adhesive film layer (also often referred to as the core layer).

[0128] In some embodiments, the multilayer adhesive assembly as described herein is in the form of a skin / core multilayer adhesive assembly, wherein the first layer is a semi-structural adhesive as described above in any of its embodiments, in some embodiments in the form of a foam, and is the core layer of the multilayer adhesive assembly, and the second adhesive layer is the skin layer of the multilayer adhesive assembly.

[0129] In some embodiments, the multilayer adhesive assembly as described herein is in the form of a multilayer adhesive assembly further comprising a third adhesive layer, forming for example a three-layer multilayer adhesive assembly. In some embodiments, the third adhesive layer is adjacent to the first adhesive layer on a side of the first adhesive layer opposite to the side of the first adhesive layer adjacent to the second adhesive layer. In some embodiments, the first adhesive layer, the second adhesive layer, and the third adhesive layer are stacked.

[0130] In some embodiments, the multilayer adhesive assembly is in the form of a skin / core / skin multilayer adhesive assembly, wherein the first adhesive layer is a semi-structural adhesive as described above in any of its embodiments in the form of a foam, and is the core layer of the multilayer adhesive assembly, the second adhesive layer is the first skin layer of the multilayer adhesive assembly, and the third adhesive layer is the second skin layer of the multilayer adhesive assembly.

[0131] The second adhesive layer and / or the third adhesive layer can have any composition generally known in the art. Thus, the composition of these individual layers for the multilayer adhesive assembly of the present disclosure is not particularly limited.

[0132] In some embodiments, the second adhesive layer and / or the third adhesive layer comprise a polymeric matrix material independently selected from the group consisting of polyacrylates, polyurethanes, polyolefins, polyamines, polyamides, polyesters, polyethers, polyisobutylenes, polystyrenes, polyethylenes, polyvinylpyrrolidones, natural rubbers, synthetic rubbers, and any combination, copolymer or mixture thereof. In some embodiments, the second adhesive layer and / or the third adhesive layer comprise a polymeric matrix material selected from the group consisting of polyacrylates, polyurethanes, and any combination, copolymer or mixture thereof. In some embodiments, the second adhesive layer and / or the third adhesive layer comprise a polymeric matrix material selected from the group consisting of polyacrylates, and any combination, copolymer or mixture thereof.

[0133] In some embodiments, the second adhesive layer and the third adhesive layer independently comprise a polyacrylate polymeric matrix material as described above for the pressure sensitive adhesive (meth)acrylate copolymer or semi-structural adhesive composition. In some embodiments of the multilayer adhesive assembly of the present disclosure, the second adhesive layer and / or the third adhesive layer have the same or similar (co)polymer composition as described above for the semi-structural adhesive of the present disclosure. In some embodiments of these embodiments, the second adhesive layer and / or the third adhesive layer do not contain fillers and / or are not foamed.

[0134] According to some aspects of the multilayer adhesive assembly of the present disclosure, the second adhesive layer and / or the third adhesive layer further comprises a tackifying resin, in particular a hydrocarbon tackifying resin. The tackifying resin can be any of the tackifying resins described above. Advantageously, the tackifying resin is selected from the group consisting of C5-based hydrocarbon resins, C9-based hydrocarbon resins, C5 / C9-based hydrocarbon resins, and any combination or mixture or hydrogenated variant thereof.

[0135] In some embodiments of the multilayer adhesive assembly of the present disclosure, the polymerizable material used to produce the second adhesive layer and / or the third adhesive layer comprises 50 to 99.5 wt% or 60 to 95 wt% of a linear or branched alkyl (meth)acrylate as a first / primary monomer, wherein the primary monomer is in some embodiments selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, and butyl acrylate; optionally, 1.0 to 50 wt%, 3.0 to 40 wt%, 5.0 to 35 wt%, or 10 to 30 wt% of a high Tg monomer as described above in any of its embodiments; optionally, 0.1 to 15 wt%, 0.5 to 15 wt%, 1.0 to 10 wt%, 2.0 to 8.0 wt%, 2.5 to 6.0 wt%, or 3.0 to 6.0 wt% of a polar monomer, such as a polar (meth)acrylate; and optionally a tackifying resin, wherein the weight percentages are based on the total weight of the polymerizable material used to produce the second adhesive layer and / or the third adhesive layer.

[0136] According to an advantageous aspect of the multilayer adhesive assembly of the present disclosure, the second adhesive layer and / or the third adhesive layer comprises a polymeric matrix material further comprising a chlorinated polyolefin (co)polymer. Incorporation of a chlorinated polyolefin (co)polymer in the curable precursor of the second adhesive layer and / or the third adhesive layer can improve the stability of the resulting adhesive layer, in particular upon hot bond aging and hot / wet bond aging on low surface energy (LSE) substrates. In some embodiments, the second adhesive layer and / or the third adhesive layer is free of a chlorinated polyolefin (co)polymer.

[0137] Examples of suitable chlorinated polyolefin (co)polymers for use herein include those sold under the trade designations "CPO 343-1" sold by Eastman Chemical Company; "13-LP", "15-LP", "16-LP", and "17-LP" sold by Toyo Kasei Kogyo Co. Ltd; "HYPALON CP 827B", "HYPALON CP 163", and "HYPALON CP 183" sold by DuPont; and "TYRIN CPE 4211P", "TYRIN CPE 6323A", and "TYRIN CPE 3615P" sold by The Dow Chemical Company. Suitable chlorinated polyolefins include chlorinated polypropylene, chlorinated polyethylene, chlorinated ethylene / vinyl acetate copolymers, and any combinations, mixtures, or copolymers thereof. In some embodiments, the chlorinated polyolefin (co)polymer is a chlorinated polypropylene.

[0138] In some embodiments, the multilayer adhesive assembly as described above in any of the embodiments of the multilayer adhesive assembly is obtained by a wet-on-wet coating process step. Exemplary "wet-in-wet" production processes for use herein are described in, for example, WO-A1-2011094385 (Hitschmann et al.) or EP-A1-0259094 (Zimmerman et al.). In some embodiments, the method for manufacturing the multilayer adhesive assembly comprises a wet-on-wet coating process step.

[0139] According to another aspect, the present disclosure discloses a method for manufacturing a multilayer adhesive assembly as described above in any of the embodiments of the multilayer adhesive assembly, wherein the method comprises superimposing a (liquid) precursor of the first adhesive layer, a (liquid) precursor of the second adhesive layer, and optionally a (liquid) precursor of the third adhesive layer, thereby forming a curable precursor of the multilayer adhesive assembly; and in some embodiments, curing the curable precursor of the multilayer adhesive assembly with actinic radiation.

[0140] In some embodiments of the method for manufacturing the multilayer adhesive assembly, the (lower) layers of the curable (liquid) precursor of the second adhesive layer are each covered by an adjacent (upper) layer of the curable liquid precursor of the first adhesive layer, substantially without exposing the (lower) layers of the curable (liquid) precursor of the second adhesive layer.

[0141] In some embodiments, the multilayer adhesive assembly is manufactured by a continuous and self-metering method for manufacturing a multilayer adhesive assembly. In some of these embodiments, the method comprises providing two or more coating knives that are independently biased from the substrate to form a gap normal to the surface of the substrate; moving the substrate in a downstream direction relative to the coating knives; and providing a curable (liquid) precursor of a first adhesive layer, a curable (liquid) precursor of a second adhesive layer, an optional curable (liquid) precursor of a third adhesive layer to the upstream side of the coating knives, thereby coating the two or more curable liquid precursors as superimposed layers onto the substrate through the respective gaps. The practice of the continuous and self-metering method for manufacturing a multilayer adhesive assembly as described above, in particular the suitable setup and configuration of the coating equipment, coating knives and coating stations for the method of manufacturing a multilayer adhesive assembly of this particular aspect, is well within the capabilities of the person skilled in the art in view of the disclosure of the present disclosure and of U.S. Patent Application Publication No. 2013 / 0004694 (Hitschmann et al.).

[0142] In some embodiments of the method for manufacturing a multilayer adhesive assembly, the first adhesive layer, the second adhesive layer and the optional third adhesive layer are prepared separately and subsequently laminated to each other. In other embodiments of the method for manufacturing a multilayer adhesive assembly, the method comprises a (co)extrusion processing step. In other embodiments of the method for manufacturing a multilayer adhesive assembly, the method comprises sequentially coating liquid compositions each comprising at least one photo-polymerizable monomer onto a substrate as described in U.S. Patent No. 4,818,610 (Zimmerman et al.). A liner can be attached to the top layer and the plurality of superimposed layers are cured by subjecting them to irradiation in order to provide an adhesive tape.

[0143] An adhesive film comprising the pressure sensitive adhesive or semi-structural adhesive described above in any of its embodiments can be conveniently coated on a liner or between liners, which can be treated with a release coating. Any suitable material for the liner and release coating can be used. In some embodiments, the adhesive film can be coated on a liner having different release properties on each surface, and optionally wound into a roll.

[0144] As described above in any of its embodiments, the make and adhesive tape of the adhesive system of the present disclosure can be applied to a variety of substrates. The substrate can be flexible or inflexible and formed of a polymeric material, a glass or ceramic material, a metal, or a combination thereof. Suitable polymeric substrates include polymeric films such as those made from polypropylene, polyethylene, polyvinyl chloride, polyesters (polyethylene terephthalate or polyethylene naphthalate), polycarbonate, poly(methyl) methacrylate (PMMA), cellulose acetate, triacetate cellulose, and ethyl cellulose. Foam substrates can be used. Examples of other substrates include metals such as stainless steel, metal or metal oxide coated polymeric materials, and metal or metal oxide coated glass.

[0145] In the context of the present disclosure, the expression "low surface energy substrate" refers to those substrates having a surface energy of less than 34 dynes / cm. The expression "medium surface energy substrate" means those substrates having a surface energy comprised between 34 dynes / cm and 70 dynes / cm, typically between 34 dynes / cm and 60 dynes / cm, and more typically between 34 dynes / cm and 50 dynes / cm. The expression "high surface energy substrate" means those substrates having a surface energy of more than 350 dynes / cm, typically more than 400 dynes / cm, and more typically those substrates having a surface energy comprised between 400 dynes / cm and 1100 dynes / cm. The surface energy is typically determined from contact angle measurements as described for example in ASTM D7490-08.

[0146] The adhesive films and multilayer adhesive assemblies of the present disclosure can be useful to form strong bonds to low surface energy (LSE) substrates. Such materials include polypropylene, polyethylene (e.g., high density polyethylene or HDPE), blends of polypropylene (e.g., PP / EPDM, TPO), or even some clear-coat surfaces. Other substrates can also have low surface energy characteristics due to the presence of residues (such as oily residues) or films (such as paint) on the surface of the substrate.

[0147] The adhesive films and multilayer adhesive assemblies of the present disclosure can also be useful to bond to medium surface energy (MSE) substrates such as for example polyamide 6 (PA6), acrylonitrile butadiene styrene (ABS), polycarbonate (PC) / ABS blends, PC, PVC, polyurethane (PUR), thermoplastic elastomers (TPE), polyoxymethylene (POM) polystyrene, poly(methyl methacrylate) (PMMA), some clear-coat surfaces (in particular clear-coat for vehicles such as cars or coated surfaces for industrial applications), and composites such as fiber reinforced plastics.

[0148] The adhesive films and multilayer adhesive assemblies of the present disclosure can also be used to bond higher surface energy (HSE) substrates such as, for example, ceramics, glass, and metals.

[0149] Accordingly, the present disclosure is further directed to the use of the adhesive systems as described above for bonding to low surface energy substrates, medium surface energy substrates, and / or high surface energy substrates.

[0150] The adhesive systems of the present disclosure can be used in any conventionally known article of manufacture that uses such assemblies, such as labels, tapes, signs, covers, marker signs, display components, and touch panels.

[0151] The method of manufacturing a bonded article can include applying a primer composition to a surface of a first substrate, and then applying an adhesive tape to the primer composition on the surface of the first substrate. The primer composition can be allowed to sit on the substrate for at least 5 minutes, 10 minutes, 15 minutes, 30 minutes, or 60 minutes prior to applying the adhesive tape. In some embodiments, the adhesive tape is a double-coated tape. In some embodiments, the method further includes applying a primer composition to a surface of a second substrate, and applying an adhesive tape to the primer composition on the surface of the second substrate, thereby adhering the first substrate to the second substrate. In some embodiments, the adhesive tape is a pressure sensitive adhesive. In some embodiments, the adhesive tape is a semi-structural tape.

[0152] The primer composition and adhesive tape of the adhesive systems of the present disclosure can be coated / applied on a substrate using any conventional coating technique modified to suit the particular substrate. For example, the primer composition can be applied / coated to various solid substrates by methods such as roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, and die coating. These various coating methods allow the primer composition to be placed on the substrate in variable thicknesses, thereby allowing for a wider range of use of the adhesive system.

[0153] The substrates to which the primer composition and adhesive tape of the present disclosure can be applied are selected depending on the particular application. For example, the primer composition and adhesive tape can be applied to sheeting products (e.g., decorative graphics and retroreflective products), label stock, and tape backing. Additionally, the adhesive films and multilayer adhesive assemblies of the present disclosure can be applied directly to other substrates, such as metal panels (e.g., automotive panels) or glass windows, such that another substrate or object can be attached to the panel or window. Accordingly, the adhesive films and multilayer adhesive assemblies of the present disclosure can be particularly useful in the automotive manufacturing industry (e.g., for attachment of exterior trim or for weather stripping), the construction industry, or the solar panel construction industry.

[0154] Accordingly, the present disclosure further relates to the use of the adhesive systems of the present disclosure for industrial applications, particularly for construction applications, automotive applications (e.g., including special purpose vehicles such as trucks, trains, and buses), appliances, cladding, and displays.

[0155] As noted above, the adhesive tape generally adheres to the primed surface of the substrate when applied without the use of heat or radiation. The adhesive tape generally adheres to the primed surface of the substrate without forming covalent bonds. Advantageously, no crosslinking agents or reactive chemicals are needed in the adhesive tape to enhance the adhesive strength. Thus, the adhesive tape generally does not include thermal crosslinking additives such as polyfunctional aziridines, isocyanates, or epoxides or chemical crosslinking agents such as peroxides. Also, the adhesive tape generally does not include photochemical crosslinking additives that are activated after application to the substrate. In some embodiments, the adhesive tapes of the present disclosure do not include polyfunctional aziridines, polyfunctional isocyanates, polyfunctional epoxides, benzophenones, triazines, polyfunctional carboxylates, oxetanes, or oxazolines.

[0156] As shown in the examples below, the adhesive systems of the present disclosure can provide excellent adhesion to a variety of substrates, resulting in cohesive failure of the adhesive tape or adhesive failure of at least 50 N / cm in embodiments of the semi-structural tape. Cohesive failure in the adhesive tapes as shown in Examples 19-30 indicates that the adhesion to the primer is stronger than the cohesive forces within the tape. In some embodiments, the use of solvents in the primer composition improves adhesion, particularly to MSE or LSE substrates. See, for example, the comparison of Example 9 to Example 10 and the comparison of Example 11 to Example 12. While the present disclosure is not bound by theory, it is believed that the solvent can lower the surface tension of the primer composition and help the primer composition wet the MSE or LSE surface. It can also help film formation of the polymers in the primer composition.

[0157] Some embodiments of the present disclosure

[0158] In a first embodiment, the present disclosure provides a primer composition comprising a polyacrylate dissolved or dispersed in water, the polyacrylate comprising, based on the total weight of monomeric units in the polyacrylate: at least 20 weight percent of methyl methacrylate units, at least 15 weight percent of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, at least 15 weight percent of acrylic monomeric units comprising an alkyl group having at least four carbon atoms, and a content of 2.5 weight percent to 10 weight percent of acrylic monomeric units comprising a carboxylic acid group. In a second embodiment, the present disclosure provides the primer composition according to the first embodiment, wherein the monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide include at least one of: 2-(N,N-dimethylaminoethyl) (meth)acrylate, 2-(N,N-diethylaminoethyl) (meth)acrylate, 2-(tert-butylaminoethyl) (meth)acrylate, 2-(N,N-dimethylaminoethyl) (meth)acrylamide, 2-(N,N-diethylaminoethyl) (meth)acrylamide, 2-(tert-butylaminoethyl) (meth)acrylamide, N-(meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidone. In a third embodiment, the present disclosure provides the primer composition according to the first or second embodiment, wherein the methyl methacrylate units, the monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, the acrylic monomeric units comprising an alkyl group having at least four carbon atoms, and the acrylic monomeric units comprising a carboxylic acid group collectively comprise at least 95 weight percent of the monomeric units in the polyacrylate. In a fourth embodiment, the present disclosure provides the primer composition according to any one of the first through third embodiments, wherein the methyl methacrylate units are present in an amount of 25 weight percent to 65 weight percent, wherein the monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide are present in an amount of 15 weight percent to 40 weight percent, wherein the acrylic monomeric units comprising an alkyl group having at least four carbon atoms are present in an amount of 15 weight percent to 40 weight percent, and wherein the acrylic monomeric units comprising a carboxylic acid group are present in an amount of 3 weight percent to 7 weight percent, based on the total weight of monomeric units in the polyacrylate. In a fifth embodiment, the present disclosure provides the primer composition according to any one of the first through fourth embodiments, further comprising at least one of a humidity stabilizer, an adhesion promoter, or a wetting agent. In a sixth embodiment, the present disclosure provides the primer composition according to any one of the first through fifth embodiments, further comprising a polyamide.In a seventh implementation, the present disclosure provides the primer composition of the sixth implementation, wherein the polyamide comprises a reaction product of a dimer acid, an oxyalkylenediamine, an additional diamine comprising at least one of a primary diamine or a secondary diamine, and a sulfonate-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic ester, or a diamine. In an eighth implementation, the present disclosure provides the primer composition of the seventh implementation, wherein the molar fraction of the dimer acid is 0.40 to 0.99, the molar fraction of the sulfonate-functional monomer is 0.01 to 0.20, and the molar fraction of at least one second dimer acid is 0 to 0.60, each based on the total moles of the combination of dimer acid, at least one second dimer acid, and any sulfonate-functional dicarboxylic acid or dicarboxylic ester; and wherein the molar fraction of the oxyalkylenediamine is 0.005 to 0.10 and the molar fraction of the at least one second diamine is 0.90 to 0.995, each based on the total moles of the combination of oxyalkylenediamine, additional diamine, and any sulfonate-functional diamine. In a ninth implementation, the present disclosure provides the primer composition of any of the first through eighth implementations, further comprising a solvent. In a tenth implementation, the present disclosure provides the primer composition of the ninth implementation, wherein the solvent comprises at least one of propylene carbonate, an alcohol, a polyol, a polyol ether, a polyol ether ester, or a dibasic ester. In an eleventh implementation, the present disclosure provides the primer composition of the tenth implementation, wherein the solvent comprises at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a dibasic ester. In a twelfth implementation, the present disclosure provides use of the primer composition of any of the first through tenth implementations as a primer for an adhesive tape.

[0159] In a thirteenth implementation, the present disclosure provides a primer composition comprising a polymer and a solvent dispersed in water, wherein water comprises at least 50 wt% of the primer composition. In a fourteenth implementation, the present disclosure provides the primer composition of any of the thirteenth implementation, wherein the solvent comprises at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a diester. In a fifteenth implementation, the present disclosure provides the primer composition of any of the tenth implementation, the eleventh implementation, the thirteenth implementation, or the fourteenth implementation, wherein the solvent comprises at least 2 wt% and no greater than 25 wt% of the primer composition. In a sixteenth implementation, the present disclosure provides the primer composition of the thirteenth implementation, the fourteenth implementation, or the fifteenth implementation, wherein the primer composition comprises at least one of a polyamide, a polyurethane, or a polyacrylate, or at least one of a polyamide or a polyacrylate. In a seventeenth implementation, the present disclosure provides the primer composition of the sixteenth implementation, wherein the primer composition comprises a polyacrylate of any of the first implementation through the fourth implementation. In an eighteenth implementation, the present disclosure provides the primer composition of any of the thirteenth implementation through the seventeenth implementation, wherein the primer composition comprises a polyamide. In a nineteenth implementation, the present disclosure provides the primer composition of the eighteenth implementation, wherein the polyamide comprises a reaction product of a dimer acid, an oxyalkylene diamine, an additional diamine comprising at least one of a primary diamine or a secondary diamine, and a sulfonate-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic acid ester, or a diamine. In a twentieth implementation, the present disclosure provides the primer composition of the nineteenth implementation, wherein a mole fraction of the dimer acid is 0.40 to 0.99, a mole fraction of the sulfonate-functional monomer is 0.01 to 0.20, and a mole fraction of at least one second dimer acid is 0 to 0.60, each based on a total number of moles of a combination of the dimer acid, the at least one second dimer acid, and any sulfonate-functional dicarboxylic acid or dicarboxylic acid ester; and wherein a mole fraction of the oxyalkylene diamine is 0.005 to 0.10 and a mole fraction of the at least one second diamine is 0.90 to 0.995, each based on a total number of moles of a combination of the oxyalkylene diamine, the additional diamine, and any sulfonate-functional diamine. In a twenty-first implementation, the present disclosure provides the primer composition of any of the thirteenth implementation through the twentieth implementation, further comprising at least one of a humidity stabilizer, an adhesion promoter, or a wetting agent. In a twenty-second implementation, the present disclosure provides use of the primer composition of any of the thirteenth implementation through the twenty-first implementation as a primer for an adhesive tape.

[0160] In a twenty-third implementation, the present disclosure provides an adhesive system comprising the primer composition of any one of the first through eleventh or thirteenth through twenty-first implementations and an adhesive tape. In a twenty-fourth implementation, the present disclosure provides the adhesive system of the twenty-third implementation, wherein the primer composition is not a component of the adhesive tape. In a twenty-fifth implementation, the present disclosure provides the adhesive system of the twenty-third or twenty-fourth implementation, wherein the adhesive tape comprises at least one of an acrylic adhesive or a rubber adhesive. In a twenty-sixth implementation, the present disclosure provides the adhesive system of any one of the twenty-third through twenty-fifth implementations, wherein the adhesive tape is a pressure sensitive adhesive tape. In a twenty-seventh implementation, the present disclosure provides the adhesive system of any one of the twenty-third through twenty-fifth implementations, wherein the adhesive tape is a semi-structural adhesive tape. In a twenty-eighth implementation, the present disclosure provides the adhesive system of the twenty-seventh implementation, wherein the semi-structural tape comprises an adhesive film comprising a first (meth)acrylate copolymer comprising at least 55 weight % of linear or branched alkyl (meth)acrylate monomer units based on the weight of the first (meth)acrylate copolymer, 15 weight % to 40 weight % of (meth)acrylic acid monomer units based on the weight of the first (meth)acrylate copolymer, wherein if the first (meth)acrylate copolymer comprises 15 weight % of (meth)acrylic acid monomer units, the first (meth)acrylate copolymer comprises at least 5 weight % of high T g monomer units of the monomer, the high T gmonomer units of crosslinking monomers having more than one (meth)acrylate group based on the weight of the first (meth)acrylate copolymer. In a twenty-ninth embodiment, the present disclosure provides the adhesive system of the twenty-eighth embodiment, wherein the first (meth)acrylate copolymer comprises 17 to 20 weight percent or 17 to 19.5 weight percent of (meth)acrylic monomer units. In a thirtieth embodiment, the present disclosure provides the adhesive system of the twenty-eighth or twenty-ninth embodiment, wherein the first (meth)acrylate copolymer comprises at least 0.15, 0.20, 0.25, 0.30, 0.40, 0.50, 0.60, or 0.70 weight percent of monomer units of crosslinking monomers having more than one (meth)acrylate group based on the weight of the first (meth)acrylate copolymer. In a thirty-first embodiment, the present disclosure provides the adhesive system of any one of the twenty-eighth through thirtieth embodiments, wherein the adhesive film comprises no more than 5 weight percent of an additional (meth)acrylate copolymer comprising 0.1 to 15 weight percent of (meth)acrylic monomer units based on the weight of the additional (meth)acrylate copolymer. In a thirty-second embodiment, the present disclosure provides the adhesive system of any one of the twenty-third through thirty-first embodiments, wherein the adhesive tape or adhesive film comprises a foam. In a thirty-third embodiment, the present disclosure provides the adhesive system of any one of the twenty-eighth through thirty-second embodiments, wherein the semi-structural adhesive tape is a multi-layer adhesive assembly comprising a first layer of the first (meth)acrylate copolymer and a second adhesive layer adjacent to the first layer. In a thirty-fourth embodiment, the present disclosure provides the adhesive system of the thirty-third embodiment, wherein the first layer of the first (meth)acrylate copolymer is a core of a skin-core-skin multi-layer adhesive. In a thirty-fifth embodiment, the present disclosure provides the adhesive system of any one of the twenty-eighth through thirty-fourth embodiments, wherein the adhesive film further comprises a second (meth)acrylate copolymer comprising greater than 15 to 40 weight percent of (meth)acrylic monomer units based on the weight of the second (meth)acrylate copolymer. In a thirty-sixth embodiment, the present disclosure provides the adhesive system of the thirty-fifth embodiment, wherein the first (meth)acrylate copolymer is present in a range of 65 to 99 weight percent based on the total weight of the adhesive film, and wherein the second (meth)acrylate copolymer is present in a range of 1 to 35 weight percent.In a thirty-seventh implementation, the present disclosure provides the adhesive system of any one of the twenty-third implementation through the thirty-sixth implementation, wherein the adhesive tape does not react with the primer composition to form a covalent bond.

[0161] In a thirty-seventh implementation, the present disclosure provides a method of manufacturing a bonded article, the method comprising applying the primer composition of any one of the first implementation through the eleventh implementation or the thirteenth implementation through the twenty-first implementation to a surface of a first substrate, and applying a semi-structural tape to the primer composition on the surface of the first substrate. In a thirty-eighth implementation, the present disclosure provides the method of the thirty-seventh implementation, wherein the semi-structural tape is a double-sided tape, the method further comprising applying the primer composition to a surface of a second substrate, and applying the semi-structural tape to the primer composition on the surface of the second substrate, thereby adhering the first substrate to the second substrate. In a thirty-ninth implementation, the present disclosure provides the method of the thirty-seventh implementation or the thirty-eighth implementation, wherein the semi-structural tape does not react with the primer composition to form a covalent bond.

[0162] The objects and advantages of the present disclosure are further illustrated by the following non-limiting examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this disclosure.

[0163] Examples

[0164] All parts, percentages, ratios, etc. in the Examples and the rest of the specification are by weight, unless otherwise indicated. The following abbreviations are used in this section: in = inch, g = gram, pph = percent, wt% = weight percent, kg = kilogram, µg = microgram, lb = pound, kN = kiloNewton, N = Newton, lb f = pound force, h = hour, min = minute, s = second, °C = degrees Celsius, °F = degrees Fahrenheit, rH = relative humidity, Hz = Hertz, mW = milliwatt, J = Joule, ° = degree, m = meter, cm = centimeter, mm = millimeter, µm = micrometer, MPa = megaPascal, psi = pound per square inch, and U / min = revolutions per minute.

[0165]

[0166] Test substrate

[0167] Adhesive tape compositions and assemblies according to the present disclosure were tested for adhesive tape properties on the following substrates.

[0168] The stainless steel (SS) sheet (“Edelstahl 1.4301 IIID”, 150mm × 50mm × 2mm) was obtained from Rocholl GmbH, Eschenbronn, Germany.

[0169] Aluminum (Al) sheet (150mm×25mm×2mm), acrylonitrile butadiene styrene (ABS) sheet (Metzoplast ABS / G, 150mm×25mm×2mm), carbon fiber reinforced plastic (CRP) sheet (150mm×25mm×2mm), glass sheet (150mm×25mm×2mm), polycarbonate sheet (150mm×25mm×2mm), powder-coated steel sheet with epoxy powder coating (150mm×25mm×2mm), polymethyl methacrylate (PMMA) sheet (150mm×25mm×2mm), and polystyrene sheet (150mm×25mm×2mm) were all obtained from Rocholl GmbH, Aglatershausen, Germany.

[0170] The polypropylene (PP) sheet (150mm×25mm×2mm) was obtained from Aquarius Plastics Ltd, Guildford, Surrey, UK.

[0171] Before testing, clean the substrate as follows. For Al and SS boards, first clean with methyl ethyl ketone (MEK) and n-heptane, dry with tissue paper, then clean with MEK and dry with tissue paper. For powder-coated boards, CRP boards, glass boards, polycarbonate boards, polystyrene boards, PMMA boards, and ABS boards, first clean with dry tissue paper applying gentle pressure to remove any residue / wax compounds from the surface, then clean with a mixture of isopropanol / distilled water (1:1) and dry with tissue paper. For PP boards, clean only with a dry towel.

[0172] Primed process : The primer was applied to the test substrate as follows. Using a pipette, the primer was placed on the end of a paper towel, allowing it to sink into the paper towel, ensuring the end was soaked but without visible excess primer on the top. The substrate was then wiped with the wet end of the paper towel to form a thin, uniform primer layer. The substrate was then exposed to air at 23°C and 50% rH for at least 5 minutes to ensure it was dry. When applied in this manner, the dry coating weight of the primer was 0.1 μg / μm. 2 Up to 1 μg / μm2 (assuming a density of 1 g / cm 3 ), resulting in layer thicknesses between 0.1 pm and 1 pm.

[0173] Test method : With 300 mm / min Conducting 90° Peel test (according to test method .Finat2 No. : A tape composition and assembly strip according to the present disclosure and having a width of 10 mm and a length of > 175 mm was cut from the sample material in the machine direction. For test sample preparation, first the liner was removed from one adhesive face and placed on an aluminum strip having the following dimensions 22 cm x 1.6 cm. Then, after removal of the liner, the adhesive coated face of each tape strip was placed with its adhesive face down on a primed test panel using a slight finger pressure. Next, the test sample was rolled in each direction two times with a standard FINAT test roller (weight 6.8 kg) at a speed of approximately 10 mm / sec to obtain intimate contact between the adhesive mass and the surface. After the adhesive composition and assembly strip was applied to the test panel, the test sample was allowed to dwell at ambient room temperature (23 °C + / - 2 °C, 50% relative humidity + / - 5%) for 24 hours or 72 hours prior to testing.

[0174] For the peel test, in a first step the test sample was clamped in the lower movable jaw of a Zwick Tensile Tester (Model Z020, commercially available from Zwick / Roell GmbH, Ulm, Germany). The adhesive film strip was folded back at an angle of 90° and the free end of the adhesive film strip was grasped in the upper jaw of the Tensile Tester in the configuration commonly used for 90° peel measurements. The Tensile Tester was set to a jaw separation rate of 300 mm / min. The test result was expressed in Newton per 10 mm (N / 10 mm). The recorded peel value was the average of two 90° peel measurements.

[0175] 750g 、 110℃ under static shear test (DIN 54516-3) FINAT Test method 8 No. 2009 Year 8 Edition)​

[0176] Static shear is a measure of the cohesiveness or internal strength of an adhesive. It is measured in units of time (minutes) required to pull down a standard area of adhesive sheet material from a test panel under a constant standard load stress.

[0177] A 25 mm wide and 12.7 mm long strip was cut from the cured adhesive sample in the machine direction. One release liner was removed from the strip and the adhesive tape sample was attached to an anodized aluminum backing through its exposed adhesive surface. Then, the second release liner was removed and the adhesive tape sample was attached to a primed test substrate using light finger pressure, providing a 25 mm x 12.7 mm bonded area. A standard FINAT test roller (6.8 kg) was rolled over the test once in each direction at approximately 10 mm per second to obtain intimate contact between the adhesive as a whole and the substrate surface. After applying the adhesive tape strip to the test panel, the test panel was left at room temperature for a period of 24 hours prior to testing. A loop was made at the end of the test strip to secure a specified weight. The test panel was placed in a shear holding device. After a dwell time of 15 min at a test temperature of 110 °C, a 750 g load was attached in the loop. The timer was started. The results were recorded in minutes and were the average of three shear measurements. A recorded time of "10000+" indicates that the adhesive did not fail after 10000 minutes.

[0178] Based on ASTM D 1002 / DIN EN 1465 single-lap shear test (lap shear test)

[0179] Overlap shear (OLS) is a measure of the cohesion or internal strength of an adhesive. 1 inch x 2 inch x 0.064 inch (2.5 cm x 5 cm x 1.1 mm) aluminum substrates supplied by Rocholl GmbH, Eschelbronn, Germany were washed with MEK, then grid blasted and cleaned with MEK, followed by air drying for 10 min. The substrates were then primed. Priming was done by a paper towel supplied by 3M Company such that approximately two inches were coated. The primed substrates were allowed to air dry for a minimum of ten minutes prior to adhesive application. Test specimens were prepared by cutting 1 inch (2 cm) strips of adhesive. One liner was removed and the adhesive was laid onto the primed portion of the substrate. A 2 inch (5.1 cm) firm rubber roller was used to ensure complete contact of the adhesive. The bond was formed by removing the top release liner exposing the adhesive and introducing it into the second primed substrate. The closed bond was then subjected to an applied pressure of approximately 150 N for 30 seconds and the bonded test assembly was left at room temperature (23 °C + / - 2 °C, 50% relative humidity + / - 5%) for 3 days prior to testing. Dynamic overlap shear testing was performed at 23 °C using a Zwick Tensile Tester (Model Z020, commercially available from Zwick / Roell GmbH, Ulm, Germany). The test sample was loaded into the grips and the crosshead was operated at 1 inch / minute, thereby loading the sample to failure. The breaking stress was recorded in units of MPa using the test method disclosed in ASTM D1002.

[0180] Shear storage modulus

[0181] A strain controlled rheometer (model ARES G2, available from TA Instruments (159 Lukens Drive, New Castle, DE 19720, USA) equipped with a parallel plate geometry (8 mm) in oscillatory shear mode at a constant frequency of 1 Hz was used. A sample cut in a circular mouthpiece of 8 mm diameter and 0.6 mm thickness was exposed to a temperature ramp from -50 °C to +150 °C applying a heating rate of 5 °C / min. The oscillatory strain and normal force control were adjusted in such a way that proper contact between the sample and the measuring geometry as well as the extent of deformation within the linear viscoelastic region of the sample material was maintained throughout the temperature range. The glass transition was determined as the peak temperature of the loss tangent. The complex modulus, storage modulus and loss tangent were monitored throughout the temperature range and specifically determined at 25 °C. For comparison of the band formulations, the complex modulus was evaluated. The complex modulus was determined by the storage modulus and the corresponding loss tangent tan d, which is the ratio of the loss modulus to the storage modulus, reflecting the Dahlquist criterion.

[0182] Preparation example FL-1 and preparation example SL-1

[0183] The precursors of the adhesive composition (foam layer and skin layer) were prepared by combining the monomer composition comprising C8 acrylates (2-EHA) and acrylic acid with 0.04 pph of PI 1 in a glass vessel. Before initiating the UV exposure, the mixture was flushed with nitrogen for 10 minutes and nitrogen was bubbled into the mixture throughout the time until the polymerization process was stopped by adding air to the slurry. The mixture was stirred with a propeller stirrer (300 U / min) all the time and the reaction was stopped when a viscosity of 2800 mPas to 4000 mPas (when measured with a Brookfield viscosimeter (model, city, country), T = 25 °C, spindle 4, 12 rpm) was reached. Then, the photoinitiator PI 1, the HDDA crosslinker and the HDDMA crosslinker as well as the fumed silica (FS) particles were added and mixed again. In a third step, the microspheres and the black pigment were added and the mixture was stirred with a propeller stirrer (300 U / min) for 5 minutes until the microspheres and the black pigment had dissolved / dispersed. The exact formulation of the polymerization precursor composition for the first adhesive polymer layer is listed in Table 2 below.

[0184] Preparation of acrylic copolymer : A (meth)acrylate copolymer, hereinafter referred to as Copolymer 2, was prepared as follows. Polymerization was performed using a Bϋchi Polycave stainless steel reactor (commercially available from Bϋchi Labortechnik GmbH, City, The Netherlands). In the first step of the polymerization, a Bϋchi reactor was charged with 250 grams of a mixture of EHA (80 wt%), AA (20 wt%), IOTG (0.04 wt%) and 3 ppm of "VAZO 52" initiator. The reactor was sealed and purged of oxygen, and then maintained at about 1 bar of nitrogen pressure. The reaction mixture was heated to 60°C, and then an adiabatic reaction was performed. The peak reaction temperature was 110°C. When the reaction was complete, the mixture was cooled to below 50°C. The polymerization conversion was about 35% or so.

[0185] Preparation example FL-2 : A precursor composition for FL2 was prepared by first diluting Copolymer 2 as described above in a polymerization precursor composition comprising C8 acrylate (EHA) and AA as shown in Table 2 below. The resulting composition was mixed at all times by oscillating it with a rolling work table (model LD 209, commercially available from Labortechnik Frobel, Germany) propeller stirrer (150 U / min) for about 24 hours, and mixing was stopped when a clear homogeneous mixture was obtained. Then, the photoinitiator PI 1, the HDDA crosslinker and the FS particles were added, and mixed again by oscillation for about 24 hours. In a third step, the glass bubbles (GB) were added, and the mixture was stirred with a propeller stirrer (300 U / min) for 5 minutes until the glass bubbles were dispersed.

[0186]

[0187] Preparation of semi-structural adhesive tape 1 and semi-structural adhesive tape 2

[0188] For semi-structural adhesive tape 1, the precursors of the adhesive skin layer SL-1 and the first adhesive polymeric foam core layer FL-1 were superimposed on each other in a laboratory coater according to the method described in WO-A1-2011094385 (Hitschmann et al.). Thereby, the liquid precursor of the adhesive skin layer (e.g. SL-1) was coated on the bottom and top of the adhesive polymeric foam core layer FL-1. The doctor blade height of the first doctor blade was set to 120 pm (for the adhesive skin layer SL-1) and the doctor blade height of the second doctor blade was set to 620 pm to 640 pm (for the polymeric foam core layer FL-1), both levels calculated from the substrate surface. Semi-structural adhesive tape 2 was prepared in the same way, but without superimposing a skin layer onto the polymeric foam core layer FL-2. Curing was done from both the top side and the bottom side in a UV curing table with a length of 600 cm at a line speed set to 1.30 m / min. The total irradiance of the cumulative irradiation from the top and the bottom was about 4 mW / cm2. The adhesive tapes were cut into pieces of 50 cm length and 2.5 cm width. 2 Semi-structural adhesive tape 1 comprises the foam core layer FL-1 and two skin layers SL-1. Semi-structural adhesive tape 2 comprises the foam core layer FL-2.

[0189] Preparation of polyamide To a 1 L glass resin flask equipped with a mechanical stirrer, a thermocouple, a distillation head equipped with a 100 mL receiving flask, and a nitrogen inlet / outlet, all of the raw materials listed in Table 3 were added. The contents of the flask were heated to 150 °C under a nitrogen atmosphere using a heating mantle and controller with stirring. The reaction mixture was refluxed for 60 min, then the reaction condenser cold finger was switched to distillation. Once the water release rate slowed, the batch temperature was increased to 225 °C and held overnight under N2with stirring. 100 ppm of 85% phosphoric acid was added, 20 mmHg to 30 mmHg vacuum was introduced into the flask over 5 min to 10 min, and the vacuum was held for 2 hours, then broken with nitrogen. The contents of the flask were poured into a silicone release paper lined aluminum tray. The contents were allowed to cool to room temperature naturally and collected. Typical yield was 500 g to 700 g. The mole percent composition of PA 1 was 33% PRIPOL 1013, 13.5% decanedioic acid, 3.5% DMSSIP, 29.25% piperazine, 17.5% ethylenediamine, 2.5% aminoethylpiperazine, and 0.75% JEFFAMINE ED-2003.

[0190]

[0191] Preparation of polyamide dispersion ​​According to Table 4, the amounts of polyamide, isopropanol, and deionized water shown in Table 4 were added to a flask equipped with an overhead stirrer, thermocouple, and distillation head equipped with a 500 mL receiving flask. The mixture was heated to 84 °C under nitrogen with stirring and held for 2 hours, at which time a clear solution was formed. The isopropanol was then distilled off under atmospheric conditions to give a milky white dispersion. The contents of the flask were allowed to cool to ambient temperature naturally and collected. The solid content of each sample in water was determined by a 105 °C, 1 hour evaporation test.

[0192]

[0193] Preparation of polyacrylate

[0194] Polymer 2 was prepared via solution polymerization. A 45.5 wt% solution was prepared by mixing 2 g AA, 10.5 g 2-EHA, 27.5 g MMA, and 10 g DMAEMA with 59.6 g DPGMME in a glass reactor. The mixture was degassed with nitrogen for 1 minute and heated to 65 °C. At this temperature, 0.4 g of “VAZO 67” initiator was added, and the mixture was allowed to react for 24 hours with constant stirring. After the reaction, the polymer solution was further diluted to 25% solids with DPGMME by adding 90 g DPGMME to the reactor. To make the final polymer aqueous solution, 26 g of the diluted polymer was mixed with 50 g DI water and 1 g acetic acid for 30 minutes.

[0195] Polymer 3 was prepared via solution polymerization. A 37 wt% DPGMME solution was prepared by mixing 3 g AA, 19 g 2-EHA, 13 g MMA, and 15 g 1 -Vinyl-2-pyrrolidinone with 85 g DPGMME in a glass reactor. The mixture was degassed with nitrogen for 1 minute and heated to 62 °C. At this temperature, 0.05 g of “VAZO 67” initiator was added, and the mixture was allowed to react for 24 hours with constant stirring. To make the final polymer aqueous solution, 8.78 g of the polymer solution was mixed with 25 g DI water and 0.5 g of a 32% ammonium solution for 30 minutes. Polymer 5 was produced in the same manner, with the exception that the amounts of starting materials shown in Table 5 below were used.

[0196] Polymer 4 was produced via emulsion polymerization. A 29 wt% aqueous emulsion was prepared by mixing 0.8 g AA, 4.2 g 2-EHA, 11 g MMA and 4 g DMAEMA with 52.4 g DI water and a surfactant mixture of 0.30 g "TERGITOL 15-S-30", 0.60 g "TERGITOL TMN-6" and 0.26 g "ETHOQUADC-12". The mixture was degassed with nitrogen for 1 minute and heated to 70 °C. At this temperature, 0.10 g of "VAZO V50" initiator was added and the mixture was allowed to react for 24 hours under constant stirring. The wt% of starting materials and the final concentration in water for the polymer dispersions (PD) 2 to PD 5 made from polymers 2 to 5, respectively, are shown in Table 5 below.

[0197]

[0198] Examples 1 to 18

[0199] The primer compositions were made by mixing all components shown in Tables 6 and 7 in a glass vessel and placing the glass vessel on a low profile lab orbital shaker (Ika KS 501 digital) at 100 rpm for 30 minutes.

[0200] The primers shown in Tables 6 and 7 were applied to ABS and SS substrates using a primer application procedure. Then 90° peel tests at 300 mm / min (according to Test Method. Finat No. 2) were performed at room temperature using a 24 hour dwell time using semi-structural adhesive tape 1 for Examples 1 to 14 and semi-structural adhesive tape 2 for Examples 15 to 18. The results are shown in Tables 6 and 7 below.

[0201]

[0202] The primer compositions shown in Tables 6 and 7 for Examples 4, 6 and 14 were applied to various substrates shown in Table 8 below using a primer application procedure. Then 90° peel tests at 300 mm / min (according to Test Method. Finat No. 2) were performed at room temperature using a 24 hour dwell time using semi-structural adhesive tape 1. Static shear tests and lap shear tests were also performed on aluminum substrates. The results are shown in Table 8 below.

[0203]

[0204] Adhesive system examples 19 to 30

[0205] The primer compositions shown in Tables 6 and 7 for Examples 4, 6, and 14 were applied to a variety of substrates shown in Table 9 below using a priming process. 90° peel tests (according to Test Method. Finat No. 2) at 300 mm / min were then performed using adhesive tapes from 3M Company, St. Paul, MN, under the trade designations "3M VHB TAPE LSE", "3M VHB TAPE GPH", "3M VHB TAPE 4941" (each having an acrylate-based adhesive facestock), and "3M ACRYLIC PLUS TAPE EX4011" having a non-acrylate-based adhesive facestock. The results are shown in Table 9 below.

[0206]

[0207] The foregoing description of the present disclosure is not intended to be exhaustive or to be limited to the precise steps or embodiments disclosed since additional modifications and variations thereof will be apparent to others skilled in the art from the foregoing description, whose intent is to provide an enabling disclosure of forms of the disclosure. Accordingly, the scope of the present disclosure is defined by the appended claims and their equivalents.

Claims

1. A make composition comprising a polyacrylate dissolved or dispersed in water, the polyacrylate comprising, based on the total weight of monomeric units in the polyacrylate: at least 20 weight percent of methyl methacrylate units; at least 15 weight percent of monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide; at least 15 weight percent of acrylic monomeric units comprising an alkyl group having at least four carbon atoms; and an amount of 2.5 weight percent to 10 weight percent of acrylic monomeric units comprising a carboxylic acid group.

2. The make composition of claim 1, wherein the monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide include at least one of 2-(N,N- dimethylaminoethyl)(meth)acrylate, 2-(N,N-diethylaminoethyl)(meth)acrylate, 2-(tert- butylaminoethyl)(meth)acrylate, 2-(N,N-dimethylaminoethyl)(meth)acrylamide, 2-(N,N- diethylaminoethyl)(meth)acrylamide, 2-(tert-butylaminoethyl)(meth)acrylamide, N- (meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidone.

3. The make composition of claim 1 or 2, wherein the methyl methacrylate units, the monomeric units comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide, the acrylic monomeric units comprising an alkyl group having at least four carbon atoms, and the acrylic monomeric units comprising a carboxylic acid group collectively comprise at least 95 weight percent of the monomeric units in the polyacrylate.

4. The make composition of any one of claims 1 to 3, further comprising a solvent.

5. The make composition of claim 4, wherein the solvent includes at least one of propylene carbonate, an alcohol, a polyol, a polyol ether, or a dibasic ester.

6. The make composition of any one of claims 1 to 5, further comprising a polyamide.

7. The make composition of claim 6, wherein the polyamide comprises a reaction product of a dimer acid, an oxyalkylenediamine, a further diamine comprising at least one of a primary diamine or a secondary diamine, and a sulfonate-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic ester, or a diamine.

8. A make composition comprising a polymer dispersed in water and a solvent, wherein water comprises at least 50 weight percent of the make composition, and wherein the solvent includes at least one of propylene carbonate, a polyol, a polyol ether, a polyol ether ester, or a dibasic ester.

9. The make composition of claim 8, wherein the make composition comprises at least one of a polyamide, a polyurethane, or a polyacrylate.

10. The primer composition of claim 8 or 9, wherein the primer composition comprises a polyamide, wherein the polyamide comprises the reaction product of: a dimer acid, an oxyalkylene diamine, an additional diamine comprising at least one of a primary diamine or a secondary diamine, and a sulfonate-functional monomer comprising at least one of a dicarboxylic acid or a dicarboxylic acid ester.

11. The primer composition of claim 7 or 10, wherein the molar fraction of the dimer acid is 0.40 to 0.99, the molar fraction of the sulfonate-functional monomer is 0.01 to 0.20, and the molar fraction of at least one second dimer acid is 0 to 0.60, each based on the total moles of the combination of the dimer acid, the at least one second dimer acid, and any sulfonate-functional dicarboxylic acid or dicarboxylic acid ester; and wherein the molar fraction of the oxyalkylene diamine is 0.005 to 0.10 and the molar fraction of the at least one second diamine is 0.90 to 0.995, each based on the total moles of the combination of the oxyalkylene diamine, the additional diamine, and any sulfonate-functional diamine.

12. An adhesive system comprising the primer composition of any one of claims 1 to 11 and an adhesive tape, wherein the primer composition is not a component of the adhesive tape.

13. The adhesive system of claim 12, wherein the adhesive tape is a semi-structural adhesive tape, and wherein the semi-structural adhesive tape comprises: an adhesive film comprising: a first (meth)acrylate copolymer comprising: at least 55 weight percent, based on the weight of the first (meth)acrylate copolymer, of linear or branched (meth)acrylic alkyl ester monomer units; Based on the weight of the first (meth)acrylate copolymer, 15% to 40% by weight of (meth)acrylate monomer units, wherein if the first (meth)acrylate copolymer comprises 15% by weight of (meth)acrylate monomer units, then the first (meth)acrylate copolymer comprises at least 5% by weight of high-T based on the weight of the first (meth)acrylate copolymer. g The monomer unit of the monomer, the high T g The monomers, during homopolymerization, provide a homopolymer with a glass transition temperature of at least 50°C; and 0.10 to 5 weight percent, based on the weight of the first (meth)acrylate copolymer, of monomer units of a crosslinking monomer having more than one (meth)acrylate group.

14. The adhesive system of claim 13, wherein the semi-structural adhesive tape is a multi-layer adhesive assembly comprising a first layer of the first (meth)acrylate copolymer and a second adhesive layer adjacent to the first layer.

15. A method of manufacturing a bonded article, the method comprising: applying the primer composition of any one of claims 1 to 11 to a surface of a first substrate; and applying a semi-structural tape to the primer composition on the surface of the first substrate.

16. The method of claim 15, wherein the semi-structural tape does not react with the primer composition to form a covalent bond.

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