Primer compositions, adhesive systems, and related processes

Abstract

The primer composition comprises a polyacrylate dissolved or dispersed in water. The polyacrylate comprises at least 20% by weight of methyl methacrylate units, at least 15% by weight of monomer units comprising at least one of secondary amines, tertiary amines, or tertiary amides, at least 15% by weight of acrylic monomer units comprising an alkyl group having at least four carbon atoms, and 2.5% to 10% by weight of acrylic monomer units comprising a carboxylic acid group. The primer composition comprises a polymer dispersed in water and a solvent, wherein water accounts for 50% by weight or more of the primer composition, and the solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester. The adhesive system comprises the primer composition and an adhesive tape. Furthermore, a method for producing the bonded article is also described.

Description

[Background technology]

[0001] Some tapes provide very high bonding strength to a wide range of clean substrates. In some cases, a primer may be applied before bonding to ensure maximum bonding strength, which may be desirable in certain applications.

[0002] For example, U.S. Patent No. 10,640,656 (Moren et al.) describes a primer composition that can provide adhesion between various substrates and double-sided tapes. U.S. Patents No. 9,234,122 (Schuemann et al.), No. 9,080,083 (Schuemann et al.), and No. 10,513,634 (Dietze et al.), as well as U.S. Patent Publications 2014 / 0113070 (Schuemann et al.), 2017 / 0066947 (Dietze et al.), and 2017 / 0298230 (Schuemann et al.) describe primer compositions containing acrylate copolymers. U.S. Patent No. 10,385,159 (Urbach et al.) discloses an aqueous primer composition for polycarbonates and polycarbonate blends. [Overview of the Initiative]

[0003] This disclosure provides a composition useful, for example, as a primer for adhesive tapes. The primer composition comprises a polymer and water. Due to the aqueous nature of the primer composition, it is useful for a wide range of applications. Despite being aqueous, the primer composition provides improved adhesion to a variety of substrates, as shown in the examples below. Advantageously, it provides useful adhesive properties in the primer or adhesive tape without requiring heat or radiation, or reactive chemistry.

[0004] In one embodiment, the disclosure provides a primer composition comprising a polyacrylate dissolved or dispersed in water. The polyacrylate comprises, based on the total weight of monomer units in the polyacrylate, at least 20% by weight of methyl methacrylate units, at least 15% by weight of monomer units comprising at least one of secondary amines, tertiary amines or tertiary amides, at least 15% by weight of acrylic monomer units comprising an alkyl group having at least 4 carbon atoms, and 2.5% to 10% by weight of acrylic monomer units comprising a carboxylic acid group.

[0005] In another embodiment, the disclosure provides a primer composition comprising a polymer dispersed in water and a solvent, wherein water accounts for at least 50% by weight of the primer composition. The solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester.

[0006] In another embodiment, the present disclosure provides the use of the above composition as a primer for adhesive tapes.

[0007] In another embodiment, the disclosure provides an adhesive system comprising a primer composition and an adhesive tape, wherein the primer is not typically a component of the adhesive tape. The adhesive tape may be a semi-structural adhesive tape.

[0008] In another embodiment, the Disclosure provides a method for manufacturing a bonded article. This method includes applying the above-mentioned primer composition to the surface of a first substrate and applying a semi-structural tape to the primer composition on the surface of the first substrate.

[0009] In another embodiment, the present disclosure provides articles bonded by the adhesive systems described herein and / or articles manufactured by the methods described herein.

[0010] The terms used in this specification are as follows: The terms "alkyl group" and the prefix "alkyl-(alk-)" include linear and branched groups, as well as cyclic groups, all possessing only CC and CH bonds. In some embodiments, alkyl groups have up to 30 carbon atoms (up to 20, 15, 12, 10, 8, 7, 6, or 5 carbon atoms in some embodiments) unless otherwise specified. Cyclic groups can be monocyclic or polycyclic and, in some embodiments, have 3 to 10 ring-member carbon atoms and other alkyl substituents; "Aryl" and "aromatic" include carbocyclic aromatic rings or ring systems, for example, having one, two, or three rings, possibly containing at least one heteroatom (e.g., O, S, or N) within the ring, and possibly substituted with up to five substituents, such as alkyl groups with up to four carbon atoms (e.g., methyl or ethyl), alkoxys with up to four carbon atoms, halo (i.e., fluoro, chloro, bromo, or iodine), hydroxy, or nitro groups, examples of which include phenyl, naphthyl, biphenyl, fluorenyl, and furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, and thiazolyl; The terms "acrylic" and "polyacrylate" refer to both acrylic and methacrylic polymers, oligomers, and monomers; The term "(meth)acrylic" refers to acrylic (also known in the art as acryloyl and acrylyl) and / or methacrylic (also known in the art as methacryloyl and methacrylyl); "Curing" refers to the process of forming a polymer chain from one or more monomers.

[0011] The term "polymer" refers to a molecule having a structure that actually or conceptually consists of multiple repetitions of units derived from one or more monomers. The term "monomer" refers to a molecule with a low relative molecular weight that can combine with other molecules to form a polymer. The term "polymer" includes homopolymers and copolymers, as well as homopolymers or copolymers that can be formed in compatible blends, for example, by co-extrusion or reaction. The term "polymer" includes random, block, graft, and star-shaped polymers. The term "polymer" encompasses oligomers.

[0012] A "monomer unit" of a polymer or oligomer is a segment of the polymer or oligomer derived from a single monomer.

[0013] The term "sulfonate-functional" can be used interchangeably with "sulfonate-substituted" and refers to a compound that is substituted with a sulfonic acid, a sulfonate salt, or both.

[0014] "Dispersed" refers to a heterogeneous mixture of individual particles or droplets in water. Polymers dispersed in water include both emulsions and suspensions.

[0015] Terms such as "a," "an," and "the" are not intended to refer to a single entity, but rather to include a general class of things for which specific examples may be used to illustrate. The terms "a," "an," and "the" are used interchangeably with the term "at least one."

[0016] When a list follows the phrase "comprising at least one of", it means including any one of the items in the list, and including any combination of two or more items in the list. When a list follows the phrase "at least one ~", it means any one of the items in the list, or any combination of two or more items in the list.

[0017] The term "crosslinked" typically refers to joining polymer chains to each other by covalent bonds through crosslinking molecules or groups to form a network polymer. Crosslinked polymers are generally characterized as insoluble but can swell in the presence of a suitable solvent. The term "crosslinked" includes those that are partially crosslinked.

[0018] All numerical ranges include their endpoints and non-integer values between the endpoints, unless otherwise specified (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0019] The features and advantages of the present disclosure will be further understood by considering the detailed description and the appended claims.

Modes for Carrying Out the Invention

[0020] This disclosure provides a primer composition comprising a polyacrylate composed of monomer units. The polyacrylate contains at least 20% by weight of methyl methacrylate monomer units, based on the total weight of monomer units in the polyacrylate. In some embodiments, the primer composition contains 20% or more, 21% or more, 22% or more, 23% or more, 24% or more, or 25% or more by weight of methyl methacrylate monomer units, based on the total weight of monomer units in the polyacrylate. In some embodiments, the primer composition contains 21, 22, 23, 24, or 25% to 65% by weight, 20% to 60% by weight, 20% to 40% by weight, or 40% to 60% by weight of methyl methacrylate, based on the total weight of monomer units in the polyacrylate. Methyl methacrylate is commercially available from various suppliers and is available from Evonik Performance Materials GmbH under the trade name "VISIOMER MMA".

[0021] Polyacrylates useful in some embodiments of the primer compositions of this disclosure contain at least 15% by weight of monomer units, based on the total weight of monomer units in the polyacrylate, each monomer unit comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide. In some embodiments, these monomer units comprise at least one of a tertiary amine or a tertiary amide. In some embodiments, these monomer units comprise at least one of a secondary amine or a tertiary amine. In some embodiments, the monomer units comprising at least one of a secondary amine or a tertiary amine are represented by formula I. [ka] [wherein R1 is hydrogen, alkyl, or arylalkylenyl; R2 is alkyl or arylalkylenyl; or R1 and R2 together with the nitrogen atom to which they are bonded form a 5-membered, 6-membered, or 7-membered ring; V is alkylene or arylalkylene; W is -O- or -N(R3)-; R3 is hydrogen, alkyl, aryl, alkylarylene, or arylalkylene; R is hydrogen or methyl.] In some embodiments, R1 is hydrogen and R2 is an alkyl having up to 4 carbon atoms. In some embodiments, R1 and R2 are each independently alkyl having up to 4 carbon atoms. In some embodiments, R1 and R2 are each 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.

[0022] In some embodiments, a monomer unit comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide is an N-acryloylpiperidine unit, an N-methacryloylpiperidine unit, or a piperazine unit represented by formula II: [ka] [wherein R3 is hydrogen, alkyl, arylalkylene, or alkylcarbonyl; R is hydrogen or methyl.] In some embodiments, the monomer unit comprising the tertiary amide includes at least one of the following: N-vinyl-2-pyrrolidone unit, N-vinylpiperidone unit, or N-vinylcaprolactam unit. Any combination of these units may be useful.

[0023] In some embodiments, a monomer unit comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide includes at least one unit from among 2-(N,N-dimethylaminoethyl)(meth)acrylate, 2-(N,N-diethylaminoethyl)(meth)acrylate, 2-(t-butylaminoethyl)(meth)acrylate, 2-(N,N-dimethylaminoethyl)(meth)acrylamide, 2-(N,N-diethylaminoethyl)(meth)acrylamide, 2-(t-butylaminoethyl)(meth)acrylamide, N-(meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidone. In some embodiments, these monomer units comprise at least one unit of 2-(N,N-dimethylaminoethyl)methacrylate or 2-(N,N-dimethylaminoethyl)acrylate.

[0024] In some embodiments, the primer composition contains 16% by weight or more, 17% by weight or more, 18% by weight or more, 19% by weight or more, or 20% by weight or more of monomer units, each containing at least one of a secondary amine, tertiary amine, or tertiary amide, based on the total weight of monomer units in the polyacrylate. In some embodiments, the primer composition contains 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, or 20% to 40% by weight of monomer units, each containing at least one of a secondary amine, tertiary amine, or tertiary amide, based on the total weight of monomer units in the polyacrylate.

[0025] Polyacrylates useful in some embodiments of the primer compositions of this disclosure include, based on the total weight of monomer units in the polyacrylate, at least 15% by weight of acrylic monomer units containing an alkyl group having at least 4 carbon atoms. The alkyl group of the alkyl acrylate or methacrylate may be linear, branched, or cyclic (including polycyclic) and may have 4 to 24, 4 to 18, or 4 to 12 carbon atoms. Examples of suitable acrylic monomer units containing an alkyl group having at least four carbon atoms include 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, and undecyl (meth)acrylate. Examples include n-dodecyl acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 2-propylheptyl (meth)acrylate, stearyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, isomiristyl (meth)acrylate, isostearyl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate. Suitable monomer units also include units of mixtures of at least two or at least three structural isomers of secondary alkyl (meth)acrylates represented by formula III: [ka] [In the formula, R4 and R5 are independently C1~C 30R4 is a saturated linear alkyl group; the sum of the number of carbon atoms in R4 and R5 is 7 to 31; and R6 is H or CH3. In some embodiments, the sum of the number of carbon atoms in R4 and R5 may 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 producing and using such monomers and monomer mixtures are described in U.S. Patent No. 9,102,774 (Clapper et al.). In some embodiments, an acrylic monomer unit containing an alkyl group having at least four carbon atoms includes at least one unit from 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, and isooctyl (meth)acrylate. In some embodiments, an acrylic monomer unit containing an alkyl group having at least four carbon atoms includes a unit of 2-ethylhexyl acrylate or 2-isooctyl acrylate.

[0026] In some embodiments, the primer composition contains acrylic monomer units having at least four carbon atoms in an amount of 16% by weight or more, 17% by weight or more, 18% by weight or more, 19% by weight or more, or 20% by weight or more, based on the total weight of monomer units in the polyacrylate, including an alkyl group having at least four carbon atoms. In some embodiments, the primer composition contains acrylic monomer units having at least four carbon atoms in an amount of 15% by weight or more, 16% by weight or more, 17% by weight or more, 18% by weight or more, or 20% to 50% by weight or 20% to 50% by weight, 20% to 40% by weight, 15% to 45% by weight, 15% to 30% by weight, or 30% to 50% by weight, based on the total weight of monomer units in the polyacrylate, including an alkyl group having at least four carbon atoms.

[0027] Polyacrylates useful for the primer compositions of this disclosure contain 2.5% to 10% by weight of acrylic monomer units containing a carboxylic acid group. Examples of suitable acrylic monomers containing a carboxylic acid group that provide these monomer units include methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, β-carboxyethyl acrylate, and β-methacryloyloxyethyl hydrogen succinic acid. In some embodiments, the acrylic monomer units containing a carboxylic acid group are acrylic acid monomer units or methacrylic acid monomer units, and in some embodiments, they are acrylic acid monomer units. In some embodiments, the acrylic monomer units containing a carboxylic acid group are present in the polyacrylate in amounts of 3% to 9% by weight, 3% to 8% by weight, 3% to 7% by weight, or 4% to 6% by weight, based on the total weight of monomer units in the polyacrylate.

[0028] In some embodiments, the polyacrylate contains additional acrylic monomer units. In some embodiments, methyl methacrylate units, monomer units comprising at least one of secondary amines, tertiary amines or tertiary amides, acrylic monomer units comprising alkyl groups having at least four carbon atoms, and acrylic monomer units comprising carboxylic acid groups together constitute at least 95%, 96%, 97%, 98%, 99%, or 100% by weight of the monomer units in the polyacrylate. In some embodiments, the polyacrylate does not contain acrylic monomer units comprising hydroxyl groups, or contains only acrylic monomer units comprising hydroxyl groups in amounts of 0.5%, 0.1%, 0.05%, 0.01%, or 0.005% or less by weight, based on the total weight of monomer units in the polyacrylate. In some embodiments, the polyacrylate does not contain N-methylolacrylamide units and N-methylolmethacrylamide units, or contains only 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight, or 0.005% by weight or less of N-methylolacrylamide units and N-methylolmethacrylamide units, based on the total weight of monomer units in the polyacrylate. In some embodiments, the polyacrylate does not contain acrylic monomer units containing phosphate groups, or contains only acrylic monomer units containing phosphate groups, based on the total weight of monomer units in the polyacrylate, in amounts of 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight, or 0.005% by weight or less. In some embodiments, the polyacrylate contains no crosslinked monomer units, or contains only crosslinked monomer units, including those described below with respect to adhesive tapes, in amounts of 0.5% by weight, 0.1% by weight, 0.05% by weight, 0.01% by weight, or 0.005% by weight or less, based on the total weight of monomer units in the polyacrylate.

[0029] In some embodiments, the primer compositions useful for the primer compositions and / or adhesive systems of the present disclosure include a polyamide. In some embodiments, the polyamide includes an ionic group. In some embodiments, the polyamide includes a reaction product of a component comprising a dimer acid, a further diamine including at least one of oxyalkylenediamines, primary diamines, or secondary diamines, and a sulfonic acid-functional monomer including at least one of dicarboxylic acids, dicarboxylic acid esters, or diamines. In some embodiments, the component for preparing the reaction product includes at least one second diacid. In this specification, the term “acid” is understood to include diesters when referring to the component for the reaction product, since the two groups of a diester react with an amine to form an amide bond. The difference is that acids react with amines to form an amide bond and the byproduct water, while esters react with amines to form an amide bond and the corresponding alcohol.

[0030] Dimer acids are dimerized acids, typically dicarboxylic acids formed by dimerizing one or more unsaturated fatty acids. In some embodiments, dicarboxylic acid dimer acids are characterized by comprising at least one alkyl or alkenyl group and comprising 12 to 100 carbon atoms, 16 to 100 carbon atoms, 18 to 100 carbon atoms, 20 to 100 carbon atoms, 30 to 100 carbon atoms, 12 to 80 carbon atoms, 20 to 80 carbon atoms, 30 to 80 carbon atoms, 12 to 60 carbon atoms, 20 to 60 carbon atoms, or 30 to 60 carbon atoms, and having two carboxylic acid groups. Dimer acids can be saturated or partially unsaturated. In some embodiments, dimer acids can be dimers of fatty acids. As used herein, the phrase “fatty acid” means an organic compound composed of an alkyl or alkenyl group containing 5 to 22 carbon atoms and having a carboxylic acid group at the end. 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, dimer acids can be formed by dimerizing an 18-carbon unsaturated fatty acid, such as oleic acid or tar oil fatty acid. In some embodiments, dimer acids are at least partially unsaturated and contain 36 carbon atoms. Dimer acids are relatively high molecular weight and consist of mixtures of substituted cyclohexenecarboxylic acids of varying sizes or relatively high molecular weights, composed in various ratios, and are primarily 36-carbon dicarboxylic acid dimer acids. The component structures can be acyclic, cyclic (monocyclic or bicyclic), or aromatic, as shown in International Patent Publication PCT / IB2022 / 060487 (Kalgutkar et al.).

[0031] Dimer acids can be prepared by condensing unsaturated monofunctional carboxylic acids, such as oleic acid, linoleic acid, soybean oil acid, or tar oil acid, via their olefinic unsaturated groups in the presence of a catalyst such as acidic clay. The distribution of various structures in dimer acids (nominal C36 dibasic acids) depends on the unsaturated acid used in their preparation. Typically, oleic acid yields dicarboxylic acid dimer acids containing about 38% acyclic, about 56% monocyclic and bicyclic, and about 6% aromatic. Soybean oil acid yields dicarboxylic acid dimer acids containing about 24% acyclic, about 58% monocyclic and bicyclic, and about 18% aromatic. Tar oil acid yields dicarboxylic acid dimer acids containing about 13% acyclic, about 75% monocyclic and bicyclic, and about 12% aromatic. The dimerization process also produces trimer acids. In some embodiments, the dimer acids have a triacid content of less than 10 mol%. Commercially available dimer acid products are typically purified by distillation, resulting in a range of dicarboxylic acid content. Useful dimer acids have at least 80% dicarboxylic acid, 90% dicarboxylic acid content, or at least 95% dicarboxylic acid content. For certain applications, further purification of dimer acids by color reduction techniques, including hydrogenation of unsaturated bonds, may be advantageous, as disclosed in U.S. Patent No. 3,595,887 (Kulkarni et al.). Hydrogenated dimer acids may also provide improved oxidative stability at high temperatures. Other useful dimer acids are disclosed in the Kirk-Othmer Encyclopedia of Chemical Technology, Organic Chemicals: Dimer Acids (ISBN 9780471238966), copyright 1999-2014, John Wiley and Sons, Inc.Commercially available dicarboxylate dimer acids are, for example, available from Oleon (Simpsonville, SC) under the trade names "RADIACID 970" and "RADIACID 959," and from Cargill Inc. (Minneapolis, MN) under the trade names "PRIPOL 1006," "PRIPOL 1009," "PRIPOL 1013," "PRIPOL 1017," and "PRIPOL 1025."

[0032] In some embodiments, the dimer acid has a number-average molecular weight of at least 300 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 is 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 or less. In some embodiments, the dimer acid has a number-average molecular weight in the range of 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 may be determined using gel permeation chromatography (GPC).

[0033] In some embodiments, the mole fraction of the dimer acid 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, based on the total number of moles (e.g., the total sum of all diacides) of the combination of the dimer acid, any second diacid, and sulfonic acid functional monomers, which include at least one of the dicarboxylic acid or dicarboxylic acid ester used to form the polyamide. Based on the total number of moles of the combination of a dimer acid, any second diacid, and a sulfonic acid-functional monomer containing at least one of a dicarboxylic acid or dicarboxylic acid ester used to form the polyamide, the mole fractions of the dimer acid may be 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 or less. In some embodiments, the mole fraction of the dimer acid may be 0.40 to 0.99, 0.50 to 0.95, or 0.60 to 0.90, based on the total number of moles of the combination of a dimer acid, any second diacid, and a sulfonic acid-functional monomer containing at least one of a dicarboxylic acid or dicarboxylic acid ester used to form the polyamide.

[0034] In some embodiments, the polyamide comprises a reaction product of a component comprising a sulfonic acid-functional monomer containing at least one of a dicarboxylic acid, a dicarboxylic acid ester, or a diamine. Suitable sulfonic acid-functional monomers containing at least one of a dicarboxylic acid or a dicarboxylic acid ester include sulfonic acid-substituted phthalates, isophthalic acid, terephthalic acid, naphthalic acid, succinic acid, their esters, and combinations thereof. The counterion of the sulfonate is H +Alternatively, it may be other metal ions such as potassium, lithium, zinc, magnesium, calcium, cobalt, iron, and / or antimony. In some embodiments, the sulfonic acid-functional monomer comprises an aryl group (e.g., phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, their esters, and combinations thereof). Suitable sulfonic acid-functional monomers include sodium 5-sulfoisophthalate salt (i.e., sodium sulfate isophthalate (SSIP)) and those represented by formula IV: [ka] [In the formula, M + Examples include ammonium, sodium, lithium, or potassium, one example being the sodium salt of dimethyl 5-sulfoisophthalate (DMSSIP). Sulfonic acid-functional isophthalic and terephthalic acids and their esters are described in detail in U.S. Patent No. 3,389,549 (David).

[0035] Suitable sulfonic acid-functionalized diamines include N-(sulfonalkyl)alkylenediamines, for example, formula: H2N-R7-NH-(CH2) y -SO3 - Y + [In the formula, R7 is an alkylene having 2 to 16 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and y is an integer from 4 to 6, Y + Examples include those having H or an alkali metal, or those represented by formula V: [ka] [In the formula, n is a number from 0 to 6, and each R8 is independently selected from H and lower alkyl groups, M +[R8 is selected from H, ammonium radicals, Group I alkali metals, and Group II alkaline earth metals]. In some cases, each R8 is identical. Such sulfonic acid-functionalized diamines are described in detail in U.S. Patent No. 3,454,535 (Bodesheim et al.) and No. 3,184,436 (Magat).

[0036] In some embodiments, the mole fraction of the sulfonic acid-functional monomer is 0.01 to 0.20 based on the total number of moles of a combination of a dimer acid, any second diacid, and a sulfonic acid-functional diacid or diacid ester comprising at least one dicarboxylic acid or dicarboxylic acid ester used to form the polyamide, or based on the total number of moles of a combination of an oxyalkylenediamine, at least one second diamine, and a sulfonic acid-functional diamine used to form the polyamide. In some embodiments, the mole fraction of the sulfonic acid functional monomer is 0.01 or greater, 0.02 or greater, 0.03 or greater, 0.04 or greater, 0.05 or greater, 0.06 or greater, 0.07 or greater, 0.08 or greater, 0.09 or greater, or at least 0.10 or greater, and 0.20 or less, 0.19 or less, 0.18 or less, 0.17 or less, 0.16 or less, 0.15 or less, 0.14 or less, 0.13 or less, 0.12 or less, 0.11 or less, or 0.10 or less.

[0037] In some embodiments, the polyamide comprises a reaction product of a component containing an oxyalkylenediamine. In some embodiments, the oxyalkylenediamine is a polyoxyalkylenediamine comprising at least one of polyethylene oxide or polypropylene oxide. In some embodiments, the oxyalkylenediamine comprises both ethylene oxide units and propylene oxide units. Suitable oxyalkylenediamines include those commercially available from Huntsman Corporation (The Woodlands, TX) under the trade name "JEFFAMINE ED" (e.g., ED-600, ED-900, ED-2003, with molecular weights of approximately 600, 900, and 2000 g / mol respectively), as well as PPG-based diamines commercially available from BASF (Florham Park, NJ) under the trade name "BAXXODUR EC" (e.g., EC301, EC302, EC303), and those commercially available from Huntsman Corporation under the trade name "JEFFAMINE D".

[0038] In some embodiments, the mole fraction of oxyalkylenediamine is 0.005 to 0.10, 0.01 to 0.03, based on the total number of moles of the combination of oxyalkylenediamine, at least one second diamine, and sulfonic acid-functionalized diamines (e.g., total diamines) used to form the polyamide. In some embodiments, the mole fraction of oxyalkylenediamine is 0.005 or more, 0.006 or more, 0.007 or more, 0.008 or more, 0.009 or more, 0.010 or more, 0.012 or more, 0.015 or more, 0.017 or more, 0.020 or more, 0.022 or more, 0.025 or more, 0.027 or more, 0.030 or more, 0.032 or more, based on the total number of moles of the combination of oxyalkylenediamine, at least one second diamine, and sulfonic acid-functionalized diamines used to form the polyamide. , 0.035 or higher, 0.037 or higher, 0.040 or higher, 0.042 or higher, 0.045 or higher, 0.047 or higher, 0.050 or higher, 0.052 or higher, 0.055 or higher, 0.057 or higher, or 0.060 or higher, and 0.100 or lower, 0.095 or lower, 0.090 or lower, 0.085 or lower, 0.080 or lower, 0.075 or lower, 0.070 or lower, 0.065 or lower, 0.060 or lower, 0.055 or lower, 0.050 or lower, 0.045 or lower, 0.040 or lower, 0.035 or lower, 0.030 or lower, or 0.025 or lower.

[0039] In some embodiments, the molar ratio of oxyalkylenediamine to sulfonic acid-functional monomer is 1:10–2:1, 1:6.66–1:1, or 1:5–1:2. When the molar ratio of oxyalkylenediamine to sulfonic acid-functional monomer is less than 1:10, the dispersion tends to contain large particles, and when the molar ratio is significantly greater than 2:1, the dispersion may exhibit an excessively high viscosity consistency (e.g., hand lotion-like).

[0040] In some embodiments, the polyamide comprises a reaction product of a component comprising at least one second diamine. “At least one second diamine” is distinct from and separate from the oxyalkylenediamines and sulfonic acid-functionalized diamines described above. The at least one second diamine may be a combination of two or more different diamines (e.g., two, three, or four diamines). The at least one second diamine may be one or more secondary diamines, one or more secondary / primary hybrid diamines, one or more primary diamines, or a combination thereof. The at least one second diamine may include 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 includes a linear or branched aliphatic diamine and an alicyclic diamine. In some embodiments, the number-average molecular weight of at least one second diamine is 30 g / mol to 5000 g / mol, 30 g / mol to 500 g / mol, or 50 g / mol to 100 g / mol.

[0041] In some embodiments, at least one second diamine is represented as R10-NH-R9-NH-R10, where R9 is an arylene or alkylene, which may be linear, branched, cyclic, or a combination thereof, and may be interrupted by at least one -O-, heterocyclic, or arylene, and each R10 is independently hydrogen, aryl, arylalkylenyl, or alkyl, which may be linear, branched, cyclic, or a combination thereof, and may be interrupted by at least one -O-, or the R10 groups may together form an alkylene as part of a ring. In some embodiments, R9 is an alkylene having 2 to 16, 2 to 6, or 2 to 4 carbon atoms. Suitable alkylene groups include -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, -cyclohexylene-CH2-cyclohexylene-, -CH2CH2-O-CH2CH2-, and -CH2-furan ring-CH2-. 1,4-phenylene is another suitable alkylene group. In some embodiments, each R10 is an alkyl group having 2-8, 2-6, or 2-4 carbon atoms. Suitable alkyl groups include methyl, ethyl, isopropyl, cyclohexyl, ethoxymethyl, and methoxyethyl. Phenyl and pyridyl are other suitable aryl groups.

[0042] In some embodiments, both R10 groups are not hydrogen atoms. That is, the diamine has two secondary amino groups and can be called a secondary diamine, or it has one primary amino group and one secondary amino group and can be called a secondary / primary hybrid diamine. Suitable examples of secondary diamines include piperazine, 1,3-di-4-piperidylpropane, 4,4'-methylenebis[N-sec-butylaniline], and 4,4'-methylenebis[N-(1-methylpropyl)cyclohexaneamine]. A suitable example of a secondary / primary hybrid diamine is 2-aminoethylpiperazine. In some embodiments, no secondary / primary hybrid diamine exists. In some embodiments, the secondary / primary hybrid diamine exists such that its mole fraction is less than 0.50, or 0.40 or less, 0.30 or less, 0.20 or less, 0.10 or less, or 0.05 or less, based on the total number of moles of at least one second diamine. In some embodiments, both R10 groups are hydrogen atoms, and the diamine can be called a primary diamine. Suitable examples of primary amines include ethylenediamine, m-xylylenediamine, 1,6-hexanediamine, o-toluidine, or 1,3-benzenedimethaneamine.

[0043] In some embodiments, the mole fraction of at least one second diamine is 0.70 to 0.995, based on the total number of moles of the oxyalkylenediamine, at least one second diamine, and sulfonic acid-functionalized diamines (e.g., the total of all diamines) used to form the polyamide. In some embodiments, the mole fraction of at least one second diamine is based on the total number of moles of the oxyalkylenediamine, at least one second diamine, and sulfonic acid-functionalized diamine used to form the polyamide, and is 0.700 or higher, 0.710 or higher, 0.720 or higher, 0.730 or higher, 0.740 or higher, 0.750 or higher, 0.760 or higher, 0.770 or higher, 0.780 or higher, 0.790 or higher, 0.800 or higher, 0.810 or higher, 0.820 or higher, 0.830 or higher, 0.840 or higher, 0.850 or higher, 0.860 or higher, 0.870 or higher, 0.880 or higher, 0.890 or higher, 0.900 or higher, 0.905 or higher, 0 It is 0.910 or greater, 0.915 or greater, 0.920 or greater, 0.925 or greater, 0.930 or greater, 0.935 or greater, 0.940 or greater, 0.945 or greater, 0.950 or greater, 0.955 or greater, or 0.960 or greater, and is 0.995 or less, 0.990 or less, 0.985 or less, 0.980 or less, 0.975 or less, 0.970 or less, 0.965 or less, 0.960 or less, 0.955 or less, 0.950 or less, 0.945 or less, 0.940 or less, 0.935 or less, 0.930 or less, 0.910 or less, 0.890 or less, 0.870 or less, 0.850 or less, 0.830 or less, 0.810 or less, 0.790 or less, 0.770 or less, or 0.750 or less.

[0044] In some embodiments, the polyamide comprises a reaction product of a component containing at least one second diacid. “At least one second diacid” is distinct from and separate from the dimer acid and sulfonic acid-functional diacid or sulfonic acid-functional diacid ester described above. Suitable examples of diacids include hexanedioic acid, nonanedioic acid, decanedioic acid (i.e., sebacic acid), dodecanedioic acid, 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, and 11-aminoundecanoic acid. In some embodiments, the mole fraction of at least one second diacid is between 0 and 0.60, based on the total number of moles of the combination of the dimer acid, at least one second diacid, and sulfonic acid-functional diacid or diacid ester used to form the polyamide. In some embodiments, the mole fraction of at least one second diacid is 0 (i.e., none), or 0.01 or greater, 0.02 or greater, 0.05 or greater, 0.07 or greater, 0.10 or greater, 0.12 or greater, 0.15 or greater, 0.17 or greater, 0.20 or greater, 0.22 or greater, or 0.2, based on the total number of moles of the combination of dimer acid, at least one second diacid, and sulfonic acid-functional diacid or diacid ester used to form the polyamide. It is 5 or greater, 0.27 or greater, 0.30 or greater, 0.32 or greater, or 0.35 or greater, and is 0.60 or less, 0.58 or less, 0.57 or less, 0.56 or less, 0.55 or less, 0.54 or less, 0.53 or less, 0.52 or less, 0.51 or less, 0.50 or less, 0.47 or less, 0.45 or less, 0.42 or less, 0.40 or less, 0.37 or less, 0.35 or less, 0.32 or less, 0.30 or less, 0.27 or less, 0.25 or less, 0.22 or less, or 0.20 or less.

[0045] In some embodiments, the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the sulfonic acid-functional monomer is 0.01 to 0.20, and the mole fraction of at least one second diacid is 0 to 0.60, based on the total number of moles of the combination of dimer acid, sulfonic acid-functional monomer, and at least one second diacid used to form the ionomer polyamide. Furthermore, the mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of at least one second diamine is 0.70 to 0.995, based on the total number of moles of the combination of oxyalkylenediamine, at least one second diamine, and sulfonic acid-functional diamine used to form the ionomer polyamide. It should be understood that the sum of the mole fractions of a particular group of listed components (e.g., diacids, diamines, etc.) is 1.0.

[0046] Generally, polymerizable compositions are essentially diol-free (e.g., completely diol-free), thereby resulting in polyamides that are essentially ester-free. The presence of ester bonds in a polymer typically reduces the polymer's heat resistance and hydrolysis resistance.

[0047] In some embodiments, polymerizable compositions useful for producing polyamides contain an excess of 1.01 to 1.2 moles or 1.01 to 1.05 moles of amine. In some embodiments, polymerizable compositions useful for producing polyamides contain an equimolar (1:1) or molar excess of acid (e.g., 1.05:1). A molar excess of acid monomers results in acid-terminated polyamides, and a molar excess of amine monomers results in amine-terminated polyamides. The use of sulfonic acid-functionalized diamines may contribute to the formation of amine-terminated polyamides.

[0048] In some embodiments, the reaction products of a dimer acid, an oxyalkylenediamine, a further diamine comprising at least one of a primary or secondary diamine, a sulfonic acid-functional monomer, and an optional second diacid are represented by the following formulas VI and VII: [Chemical] [In the formula, R11 is independently a residue of a dimer acid (e.g., any of the above dimer acids) or a residue of a second diacid (e.g., any of the at least one second diacid above) in any of the above molar ratios; R12 is independently oxyalkylene or R9 in any of the above embodiments in any of the above molar ratios; R13 is alkylene, arylene, or a combination thereof, and R10 and M + are as defined in any of the above embodiments. In some embodiments, R13 is arylene.

[0049] In some embodiments, the polyamide has a glass transition temperature of 25°C or lower, 20°C or lower, 15°C or lower, 10°C or lower, 5°C or lower, 0°C or lower, -5°C or lower, -10°C or lower, -15°C or lower, -20°C or lower, -25°C or lower, -30°C or lower, and -50°C or higher. The glass transition temperature is measured by differential scanning calorimetry at a heating rate of 10 K / min.

[0050] The polyamide may be formed by a conventional condensation reaction among a dimer acid, an oxyalkylenediamine, a further diamine containing at least one of a primary diamine or a secondary diamine, a sulfonic acid functional monomer, and any at least one second diacid. In some embodiments, the condensation reaction includes refluxing of the polymerizable composition followed by distillation.

[0051] Considering at least U.S. Patent No. 3,709,865 (Lofquist et al.), it was unexpected that a polyamide as described herein could be successfully synthesized using the above components, particularly the dimer acid which tends to be hydrophobic. It was further unexpected that the polyamide described herein is useful as a primer despite its predominantly hydrophobic nature.

[0052] In some embodiments, the primer compositions of the present disclosure include polyurethane. The polyurethane may include a backbone with a variety of suitable structural arrangements. The backbone may optionally include one or more other backbone bonds (e.g., amide, ester, carbonate ester, epoxy, ether, imide, imine, or urea bonds, or combinations thereof). Furthermore, the backbone of the polyurethane polymer may optionally include one or more oligomers or polymer segments (e.g., acrylic, polyamide, polyester, poly(carbonate ester), epoxy, polyether, polyimide, polyimine, or polyurea segments, or combinations thereof). The polyurethane may be linear or substantially linear.

[0053] Polyurethanes can be formed using any suitable reactants and any suitable process. Polyurethanes are typically formed from starting materials comprising one or more isocyanates, one or more polyols, and any one or more additional reactants (e.g., those having one or more active hydrogen groups). In some cases, a stoichiometric excess of isocyanate is reacted with the polyol. For example, the ratio of isocyanate groups to hydroxyl groups may 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. Polyurethanes may have a number-average molecular weight in the range of about 1,000 to about 10,000, or about 2,500 to about 7,500.

[0054] Suitable isocyanates include those having 1, 2, 3, or 4 isocyanate groups, and mixtures thereof. Suitable diisocyanates include isophorone diisocyanates (i.e., 5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane), 5-isocyanato-1-(2-isocyanatoethi-1-yl)-1,3,3-trimethylcyclohexane, 5-isocyanato-1-(3-isocyanatoprop-1-yl)-1,3,3-trimethylcyclohexane, and 5-isocyanato-(4-isocyanatobutyl -1-yl)-1,3,3-trimethylcyclohexane, 1-isocyanato-2-(3-isocyanatoprop-1-yl)cyclohexane, 1-isocyanato-2-(3-isocyanatoethi-1-yl)cyclohexane, 1-isocyanato-2-(4-isocyanatobutyl-1-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-isocyanatonol)-1-pentylcyclohexane, 1,2-, 1,4-, and Examples include 1,3-bis(isocyanatomethyl)cyclohexane, 1,2-, 1,4-, and 1,3-bis(2-isocyanatoethi-1-yl)cyclohexane, 1,3-bis(3-isocyanatoprop-1-yl)cyclohexane, 1,2-, 1,4-, or 1,3-bis(4-isocyanatobutyl-1-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 comprises at least one of isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HMDI).In some embodiments, HMDI is the primary isocyanate used in preparing polyurethanes; in other words, there are more HMDI units than any other isocyanate units.

[0055] Suitable polyols for preparing polyurethanes include monomers, oligomers, polymers, and mixtures thereof, and include diols, triols, polyols having four or more hydroxyl groups, and mixtures thereof. Examples of polyols used as reactants or as starting materials for oligomer or polymer 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, hexylenediol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene or polypropylene glycol, isopropylidenebis(p-phenylene-oxypropanol-2), and mixtures thereof. Examples of suitable oligomer and / or polymer 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 may include any of the diol units described above and units of aromatic diacids, units of aliphatic diacids, or combinations thereof. In some embodiments, the polyester diol includes linear diol units having four or more carbon atoms and linear diacid units having four or more carbon atoms. In some embodiments, the polyester diol further includes units of phthalic acid, isophthalic acid, or terephthalic acid.

[0056] In some embodiments, monomers or oligomers having a base or salt-forming group may be included in the reactants used to produce the polyurethane, but this is not essential. In some embodiments, acid- or anhydride-functionalized salt-forming monomers, such as dimethylolpropionic acid or trimellit anhydride, are used to form the polyurethane. In some embodiments, the polyurethane contains acid- or anhydride groups (or other neutralizable groups that can form anionic salt groups), which are neutralized with tertiary amines.

[0057] Some of the polyurethanes useful for carrying out this disclosure are commercially available, for example, as emulsions from Alberdingk Boley and BASF.

[0058] The primer compositions of the present disclosure and / or primer compositions useful for the adhesive systems of the present disclosure contain water. In some embodiments, water accounts for 50% or more by weight, 55% or more by weight, 60% or more by weight, 65% or more by weight, 70% or more by weight, or 75% or more by weight of the primer composition. In some embodiments, water accounts for 95% or less by weight, 92.5% or less by weight, 90% or less by weight, 87.5% or less by weight, or 85% or less by weight of the primer composition.

[0059] In some embodiments, the primer compositions useful for the primer compositions and / or adhesion systems of the present disclosure include a solvent. In some embodiments, the useful solvent is non-flammable and has a low vapor pressure (e.g., less than 1 hectopascal (hPa) at 20°C). Examples of solvents useful for the primer compositions include polar and / or water-miscible (i.e., soluble in water in any proportion) solvents, such as monohydroxy alcohols having 1 to 8 or more carbon atoms (e.g., methanol, ethanol, isopropanol, propanol, butanol, isooctyl alcohol); polyols, such as glycols (e.g., ethylene glycol, or propylene glycol); terminal alkanediols (e.g., 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol); and polyglycols (e.g., diethylene glycol, triethylene glycol). Examples include 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 glycol ethers available under the trade name “DOWANOL” from Dow Chemical Co. (Midland, MI)); propylene carbonate; dibasic acid esters; and combinations thereof. In some embodiments, the solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester. In some embodiments, the solvent contains no or less than 1% monohydroxy alcohols having 1 to 8 or more carbon atoms, monohydroxy alcohols having 1 to 4 carbon atoms, or isopropanol.

[0060] In some embodiments, the solvent independently comprises at least one of a polyol or polyol ether having 2 to 10 carbon atoms (2 to 9 or 2 to 8 carbon atoms in some embodiments). In some embodiments, the solvent comprises a polyol. A "polyol" is an organic molecule consisting of C, H, and O atoms, where these atoms are connected to each other by CH, CC, CO, or OH single bonds, and having at least two COH 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. A "polyol ether" is an organic molecule consisting of C, H, and O atoms, where these atoms are connected to each other by CH, CC, CO, or OH single bonds, or by C=C double bonds, and is theoretically derivable by at least partial etherification of a polyol. In some embodiments, the polyol ether has at least one COH group and at least one COC bond. In some embodiments, the polyol ether has at least two COC bonds. Similarly, “polyol ether ester” refers to an organic molecule consisting of C, H, and O atoms, which are connected to each other by CH, CC, CO, OH single bonds and C=O double bonds, and which is theoretically derivable by at least partial etherification and esterification of a polyol. In some embodiments, the polyol ether ester has one COC(O)-C group and at least one COC bond. Useful polyol ethers and / or polyol ether esters may have 3 to 10, 3 to 8, or 5 to 8 carbon atoms. In some embodiments, the solvent includes at least one of propylene carbonate, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, 2-phenoxyethanol, dibasic acid ester, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, or dipropylene glycol monomethyl ether.

[0061] In some embodiments, the solvent accounts for 2% or more, 2.5% or more, 3% or more, 4% or more, or 5% or more by weight of the primer composition. In some embodiments, the solvent accounts for 25% or less, 20% or less, 15% or less, 12.5% ​​or less, or 10% or less by weight of the primer composition.

[0062] In some embodiments, the primer compositions useful for the primer compositions and / or adhesive systems of the present disclosure include a humidity stabilizer (also called a water scavenger). Examples of suitable humidity stabilizers include silanes, e.g., vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, O-methylcarbamatomethyl-methyldimethoxysilane, O-methylcarbamatomethyl-trimethoxysilane, O-ethylcarbamatomethyl-methyldiethoxysilane, O-ethylcarbamatomethyl-triethoxysilane, 3-methacryloyloxypropyl-trimethoxysilane, methacryloyloxymethyl-trimethoxysilane, methacryloyloxymethylmethyldimethoxysilane, methacryloyloxymethyl Examples include liloyloxymethyltriethoxysilane, methacryloxymethylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, acryloyloxymethyltrimethoxysilane, acryloyloxymethylmethyldimethoxysilane, acryloyloxymethyltriethoxysilane, acryloyloxymethylmethyldiethoxysilane, common alkylalkoxysilanes, 3-glycidoxypropyltrimethoxysilane, other functionalized organic silanes, and aminosilanes, which are also described later as adhesion promoters. In some embodiments, the primer composition contains 0.01% by weight or more, in some embodiments 0.03% by weight or more, and 5% by weight or less, 2% by weight or less, or 1% by weight or less of one or more humidity stabilizers.

[0063] In some embodiments, the primer compositions and / or primer compositions useful for the adhesion systems of the present disclosure include adhesion promoters. Useful adhesion promoters include those commercially available from OSI under trade names “A1120”, “A187”, and “A189”, and from Dow Chemical under trade name “Z9020”. Aminosilanes are useful as adhesion promoters. Examples of aminosilanes useful as adhesion promoters include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, Examples include 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, [Nu],[Nu]'-bis[3-trimethoxysilyl]propylethylenediamine, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, and N-phenylaminomethyltrimethoxysilane. Suitable adhesion promoters also include titanates. In some embodiments, the primer composition further comprises a titanate chelate.Examples of suitable titanate chelates include acetylacetonate titanate chelate, triethanolamine titanate chelate, and those obtained from Dorfketal GmbH in Germany under the trade name "TYZOR". In some embodiments, the primer composition contains one or more adhesion promoters in an amount of at least 0.01% by weight, and in some embodiments, at least 0.1% by weight or at least 0.5% by weight. In some embodiments, the primer composition contains one or more adhesion promoters in an amount of 5% by weight or less, and in some embodiments, at least 2% by weight.

[0064] In some embodiments, the primer compositions useful for the primer compositions of the present disclosure and / or the adhesive systems of the present disclosure include a wetting agent. Useful wetting agents include surfactants. A surfactant is a compound that, when dissolved in water or an aqueous solution, reduces surface tension, or reduces interfacial tension between two liquids, or between a liquid and a solid. Surfactants useful for the implementation of the present disclosure include cationic surfactants, anionic surfactants, zwitterionic surfactants, or nonionic surfactants. Examples of anionic surfactants include sulfonates, carboxylates, and phosphates. Examples of cationic surfactants include quaternary amines. Examples of nonionic surfactants include block copolymers containing ethylene oxide and silicone surfactants (e.g., ethoxylated alcohols, ethoxylated fatty acids, sorbitan derivatives, lanolin derivatives, ethoxylated nonylphenol, alkoxylated polysiloxanes). In some embodiments, the primer composition includes at least 0.1% by weight of one or more wetting agents, and in some embodiments, at least 0.5% by weight of one or more wetting agents. In some embodiments, the primer composition contains 5% by weight or less of one or more wetting agents, and in some embodiments, 2% by weight or less of one or more wetting agents.

[0065] In some embodiments, the primer compositions useful for the primer compositions of the present disclosure and / or the adhesive systems of the present disclosure include a pH adjuster. In some embodiments, it may be useful to adjust the pH of the aqueous phase to a range of 8 to 12 or 8 to 10. Examples of bases useful for pH adjustment include Brønsted bases such as sodium hydroxide and ammonium hydroxide, organic bases such as triethylamine, and combinations thereof. In some embodiments, it may be useful to adjust the pH of the aqueous phase to a range of 2 to 6 or 3 to 5. Examples of acids useful for pH adjustment include Brønsted acids such as hydrochloric acid, organic acids such as acetic acid, and combinations thereof.

[0066] This disclosure provides an adhesive system comprising a primer composition as described in any of the embodiments described above, in combination with an adhesive tape. In some embodiments of this disclosure, the primer composition is useful for improving the adhesion of the adhesive tape to a first substrate for bonding to a second substrate, for example. In some embodiments, the primer composition is not a component of the adhesive tape. For example, the primer composition is not placed on the tape support for the purpose of improving the adhesion between the adhesive and the support (backing). In some embodiments, the primer composition comprises a polymer dispersed in water and a solvent, with water accounting for at least 50% by weight of the primer composition. In some embodiments, the primer composition comprises at least one of polyamide, polyurethane, or polyacrylate, which are as described in any of the embodiments described above. Advantageously, heat, radiation, or reactive chemistry is not required in the primer or adhesive tape to provide favorable adhesive properties in the adhesive system of this disclosure. The adhesive tape typically adheres to the surface of a primer-treated substrate without the formation of covalent bonds. For example, the adhesive tape typically does not react with the primer composition to form covalent bonds. This adhesive system may be useful, for example, for bonding substrates.

[0067] In the adhesive system, any suitable adhesive tape can be used, and the primer composition is useful for improving the adhesion of various adhesives to the substrate. The adhesive on the adhesive tape may 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 has a multilayer adhesive structure, such as in a double-sided adhesive tape. For example, a multilayer adhesive tape may have a first adhesive skin layer, a second adhesive skin layer, and a core layer positioned between the first and second adhesive skin layers. The core layer is often a foam support layer, which may be an adhesive foam or a non-adhesive foam. In another example, a multilayer adhesive tape may have a first adhesive layer, a film support, and a second adhesive layer. The film support may be an adhesive layer or a non-adhesive layer.

[0068] In some embodiments, adhesive tapes useful in the adhesive systems of the present disclosure include pressure-sensitive adhesives based on (meth)acrylate copolymers. (Meth)acrylate copolymers typically have glass transition temperatures (Tg) of 20°C or less, 10°C or less, 0°C or less, -10°C or less, -20°C or less, -30°C or less, -40°C or less, or -50°C or less. The glass transition temperature can be measured using techniques such as differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Alternatively, the glass transition temperature can be predicted using Fox's formula based on the monomers used to form the adhesive. Lists of glass transition temperatures for homopolymers are available from several monomer suppliers, including BASF Corporation (Houston, TX, USA), Polyscience, Inc. (Warrington, PA, USA), and Aldrich (St. Louis, MO, USA), and are also reported in numerous publications, such as Mattioni et al., J. Chem. Inf. Comput. Sci., 2002, 42, 232-240, and in the Polymer Properties Database at polymerdatabase.com.

[0069] (Meth)acrylate copolymers are typically formed from monomer compositions comprising at least one low-Tg monomer. As used herein, the term "low-Tg monomer" refers to a monomer having a Tg of 20°C or less when homopolymerized (i.e., a homopolymer formed from a low-Tg monomer has a Tg of 20°C or less). 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 often non-tertiary alkyl acrylates, but may also be alkyl methacrylates having a linear alkyl group having at least four carbon atoms. Examples of alkyl (meth)acrylates include n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, s-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-octadecyl acrylate, isostearyl acrylate, and n-dodecyl methacrylate. Isomers and mixtures of these monomers can be used.

[0070] Examples of low-Tg heteroalkyl (meth)acrylate monomers often have at least 3 carbon atoms, at least 4 carbon atoms, or at least 6 carbon atoms, and can have 30 or more, 20 or less, 18 or less, 16 or less, 12 or less, or 10 or less carbon atoms. Specific examples of heteroalkyl (meth)acrylates include 2-ethoxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-methoxyethyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0071] Examples of low-Tg aryl-substituted alkyl acrylates or aryloxy-substituted alkyl acrylates include 2-biphenylhexyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, and 2-phenylethyl acrylate.

[0072] Monomer compositions for (meth)acrylate copolymers may contain polar monomers. Polar monomers have an ethylenically unsaturated group and a polar group such as an acidic group or its salt, a hydroxyl group, a primary amide group, a secondary amide group, a tertiary amide group, or an amino group. The presence of polar monomers often promotes adhesion of pressure-sensitive adhesives to various 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, β-carboxyethyl (meth)acrylate, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof. Due to their availability, acidic monomers are often acrylic acid or methacrylic acid.

[0073] Examples of polar monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate), hydroxyalkyl (meth)acrylamides (e.g., 2-hydroxyethyl (meth)acrylamide or 3-hydroxypropyl (meth)acrylamide), ethoxylated hydroxyethyl (meth)acrylates (e.g., monomers commercially available from Sartomer (Exton, PA, USA) under trade names CD570, CD571, and CD572), and aryloxy-substituted hydroxyalkyl (meth)acrylates (e.g., 2-hydroxy-2-phenoxypropyl (meth)acrylate).

[0074] 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)acrylamide, such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nt-octyl(meth)acrylamide, and N-octyl(meth)acrylamide.

[0075] Examples of polar monomers having a tertiary amide group include N-vinylcaprolactam, N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, 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.

[0076] Polar monomers containing amino groups 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.

[0077] Monomer compositions for (meth)acrylate copolymers may optionally contain high-Tg monomers. As used herein, "high-Tg monomer" means a monomer that, when homopolymerized, has a Tg of over 30°C, over 40°C, or over 50°C (i.e., the homopolymer formed from that monomer has a Tg of over 30°C, over 40°C, or over 50°C). Suitable high-Tg monomers include those having a single (meth)acryloyl group, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl (meth)acrylate, 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 various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., α-methylstyrene), vinyl halides, and mixtures thereof. Vinyl monomers having groups that characterize polar monomers are considered polar monomers in this specification.

[0078] Overall, pressure-sensitive adhesives can contain up to 100% by weight (e.g., 100% by weight) of low-Tg monomer units. The weight percentage value is based on the total weight of monomer units in the polymer material. In some embodiments, the (meth)acrylate polymer contains 40–100% by weight of low-Tg monomer units, 0–15% by weight of polar monomer units, 0–50% by weight of high-Tg monomer units, and 0–15% by weight of vinyl monomer units. In some embodiments, the (meth)acrylate polymer contains 60–100% by weight of low-Tg monomer units, 0–10% by weight of polar monomer units, 0–40% by weight of high-Tg monomer units, and 0–10% by weight of vinyl monomer units. In some embodiments, the (meth)acrylate polymer contains 75–100% by weight of low-Tg monomer units, 0–10% by weight of polar monomer units, 0–25% by weight of high-Tg monomer units, and 0–5% by weight of vinyl monomer units.

[0079] In some embodiments, adhesive tapes useful in the adhesive systems of the present disclosure include adhesives based on semicrystalline polymer resins (in some embodiments, pressure-sensitive adhesives), where the semicrystalline polymer resins are, for example, polyolefins and polyolefin copolymers (e.g., polymer resins based on monomers having 2 to 8 carbon atoms, e.g., 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-methacrylate copolymers neutralized with a base), and cellulose acetate. Other polymers useful as adhesives in adhesive tapes include amorphous polymers such as polyacrylonitrile, polyvinyl chloride, thermoplastic polyurethane, aromatic epoxy, polycarbonate, amorphous polyester, amorphous polyamide, ABS block copolymer, polyphenylene oxide alloy, ionomer (e.g., ethylene-methacrylic acid copolymer neutralized as a salt), fluorinated elastomer, and polydimethylsiloxane.

[0080] In some embodiments, adhesive tapes useful in the adhesive systems of the present disclosure include adhesives (pressure-sensitive adhesives in some embodiments) based on elastomers, such as random and block copolymers of polybutadiene, polyisoprene, polychloroprene, styrene, and dienes (e.g., SBR), and ethylene-propylene-diene monomer rubber. This type of polymer is typically combined with a tackifying resin. A block copolymer adhesive composition may include a first block copolymer comprising at least one rubbery block comprising a first polymerized conjugated diene, a hydrogenated derivative thereof, or a combination thereof, and at least one glassy block comprising a first polymerized monovinyl aromatic monomer. In some embodiments, the first block copolymer is of formula Q n-Y is a multi-armed block copolymer, where Q represents an arm of the multi-armed block copolymer, n represents the number of arms, n is an integer greater than or equal to 3, and Y is a residue of a polyfunctional coupling agent. Each arm Q independently has the formula RG, where R represents a rubbery block and G represents a glassy block. In some embodiments, the first block copolymer is a polymodal asymmetric star-type 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 second polymerized conjugated diene, its hydrogenated derivative, 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 the block copolymer further comprises a first high-Tg tackifier having a Tg of 60°C or higher, wherein the first high-Tg tackifier is compatible with 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 and being compatible with at least one glassy block.

[0081] In some embodiments, the elastomer adhesive is, for example, one described in U.S. Patent No. 9,556,367 (Waid et al.). The adhesive is a pressure-sensitive adhesive and comprises 92 to 99.9 parts of a block copolymer adhesive composition and 0.1 to less than 10 parts of an acrylic adhesive composition. The acrylic adhesive composition comprises 70 to 100 parts of at least one acrylic or methacrylic ester of a non-tertiary alkyl alcohol having 4 to 20 carbon atoms, and 0 to 30 parts of copolymerized reinforcing monomers.

[0082] In some embodiments, adhesive tapes useful in the adhesive systems of the present disclosure include adhesives based on pressure-sensitive hot-melt adhesives containing polymers prepared from non-photopolymerizable monomers. Such polymers may be adhesive polymers (i.e., polymers that are inherently adhesive) or polymers that are not inherently adhesive but can form an adhesive composition when mixed with components such as plasticizers and / or tackifying resins. Specific examples include poly-α-olefins (e.g., polyoctene, polyhexene, and atactic polypropylene), block copolymer adhesives, natural and synthetic rubbers, silicone adhesives, ethylene-vinyl acetate, and epoxy-containing structural adhesive blends (e.g., epoxy-acrylate and epoxy-polyester blends).

[0083] The adhesive contained in the adhesive tape useful in the adhesive system of this disclosure may optionally include other components such as fillers, antioxidants, viscosity modifiers, pigments (e.g., carbon black, titanium dioxide, or other suitable pigments), tackifying resins, and fibers. These components can be added to the adhesive insofar as they do not alter the desired properties of the final product.

[0084] Various commercially available adhesive tapes may be useful in the adhesive system of this disclosure. For example, the adhesive system may include adhesive tapes available from 3M Company (St. Paul, MN) under the trade name "VHB". These include the "3M VHB TAPE LSE" series, the "3M VHB TAPE GPH" series, "3M VHB TAPE 4941", and "3M VHB TAPE 4611".

[0085] In some embodiments, the adhesive tapes useful in the adhesive systems of the present disclosure include semi-structural adhesives. The semi-structural adhesives have a shear storage modulus of 0.5 megapascals (MPa) or greater when measured on a rheometer with a vibration strain of 1 Hz applied within the linear viscoelastic region of the adhesive film at 25°C. In some embodiments, the adhesives have a storage modulus of 1 MPa or greater or 1.5 MPa. In some embodiments, the adhesive films of the present disclosure have a storage modulus of 4 MPa or less, 3.5 MPa or less, 3 MPa or less, 2.5 MPa or less, or 2 MPa or less. The storage modulus of the bulk adhesive film can be easily measured by the method described in the following examples. In embodiments where the adhesive film is a multilayer film, as described in more detail below, the storage modulus can be determined by nanoindentation based on atomic force microscopy (AFM) at frequencies and temperatures in the rheologically relevant region (0.1 Hz to 100 Hz).

[0086] While the semi-structural adhesive exceeds the Dalquist standard, the adhesive system of this disclosure can provide excellent wettability to the substrate. The semi-structural adhesive can provide overlap shear strength values ​​of 2.5 MPa to 3.5 MPa, as shown in the following examples. Therefore, the adhesive film of this disclosure has excellent cohesive strength and can provide much higher overlap shear adhesion values ​​than typical pressure-sensitive adhesives.

[0087] In some embodiments, the semi-structural adhesive in the adhesive system of the present disclosure comprises a first (meth)acrylate copolymer, the first (meth)acrylate copolymer comprising, on its weight, at least 55% by weight of linear or branched alkyl (meth)acrylate monomer units. In some embodiments, the first (meth)acrylate copolymer comprises, on its weight, 60% or more, 65% or more, or 70% or more by weight of linear or branched alkyl (meth)acrylate monomer units. In some embodiments, the first (meth)acrylate copolymer comprises, on its weight, less than 85% or 84% or less, 83% or less, 82% or less, 81% or less, or 80% or less by weight of linear or branched alkyl (meth)acrylate monomer units. In some embodiments, a semi-structural adhesive useful in the adhesive system of the present disclosure comprises a second (meth)acrylate copolymer, the second (meth)acrylate copolymer comprising, based on its weight, 55% or more, 60% or more, 65% or more, or 70% or more by weight of linear or branched alkyl (meth)acrylate monomer units. In some embodiments, the second (meth)acrylate copolymer comprises, based on the weight of the first (meth)acrylate copolymer, less than 85% or 84% or less, 83% or less, 82% or less, 81% or less, or 80% or less by weight of linear or branched alkyl (meth)acrylate monomer units. In some embodiments, the linear or branched alkyl (meth)acrylate monomer units are C1-C 32 (meth)acrylic acid ester monomer unit, C1-C 24 (meth)acrylic acid ester monomer units, or C1-C 18 It is a (meth)acrylic acid ester monomer unit.

[0088] A suitable example of an alkyl (meth)acrylate is one represented by the formula CH2=C(R)COOR', where R is a hydrogen or methyl group, and R' is a linear or branched 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. Examples of suitable monomers represented by the 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 Examples include acrylates, undecyl (meth)acrylates, n-dodecyl acrylates, lauryl (meth)acrylates, tridecyl (meth)acrylates, tetradecyl (meth)acrylates, pentadecyl (meth)acrylates, hexadecyl (meth)acrylates, heptadecyl (meth)acrylates, 2-propylheptyl (meth)acrylates, stearyl (meth)acrylates, n-nonyl (meth)acrylates, isononyl (meth)acrylates, isomiristyl (meth)acrylates, isostearyl (meth)acrylates, octadecyl (meth)acrylates, and behenyl (meth)acrylates. Suitable monomer units may further include mixtures of at least two or at least three structural isomers of secondary alkyl (meth)acrylates represented by formula III as described in any of the above embodiments. In some embodiments, the first (meth)acrylate copolymer and / or optionally present second (meth)acrylate copolymer comprises at least one of 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, and isooctyl (meth)acrylate.In some embodiments, the first (meth)acrylate copolymer and / or the second (meth)acrylate copolymer comprises 2-ethylhexyl (meth)acrylate.

[0089] A first (meth)acrylate copolymer useful in the semi-structural adhesive of the adhesive system of the present disclosure contains 15% to 40% by weight of (meth)acrylic acid monomer units. In some embodiments, the first (meth)acrylate copolymer contains 15% or more, more than 15% by weight, more than 16% by weight, or more than 17% by weight of (meth)acrylic acid monomer units, based on its weight. In some embodiments, when present in the semi-structural adhesive, a second (meth)acrylate copolymer contains more than 15% to 40% by weight of (meth)acrylic acid monomer units. In some embodiments, the second (meth)acrylate copolymer contains more than 15% by weight, more than 16% by weight, or more than 17% by weight of (meth)acrylic acid monomer units, based on its weight. In some embodiments, the first (meth)acrylate copolymer in the semi-structural adhesive contains, on weight, 15.5–40% by weight, 16–40% by weight, 16–35% by weight, 16–30% by weight, 16–25% by weight, 17–25% by weight, 17–23% by weight, 17–20% by weight, or 17–19.5% by weight of (meth)acrylic acid monomer units. In some embodiments, the second (meth)acrylate copolymer optionally present in the semi-structural adhesive contains, on weight, 15.5–40% by weight, 16–40% by weight, 16–35% by weight, 16–30% by weight, 16–25% by weight, 17–25% by weight, 17–23% by weight, or 17–20% by weight of (meth)acrylic acid monomer units. Examples of (meth)acrylic acid monomer units include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, ethacrylic acid, crotonic acid, citraconic acid, cinnamic acid, β-carboxyethyl acrylate, and 2-methacryloyloxyethyl succinate. In some embodiments, the (meth)acrylic acid monomer unit is either an acrylic acid monomer unit or a methacrylic acid monomer unit. The (meth)acrylic acid monomer unit includes salts of these acids, such as alkali metal salts and ammonium salts.

[0090] In some embodiments, the first (meth)acrylate copolymer of a semi-structural adhesive useful in the adhesive system of the present disclosure further comprises monomer units of a “high Tg” monomer that, when polymerized, provides a homopolymer having a glass transition temperature (Tg) of 50°C or higher, 60°C or higher, or 70°C or higher (i.e., the homopolymer formed from its monomer has a Tg of 50°C or higher, 60°C or higher, or 70°C or higher). In embodiments in which the first (meth)acrylate copolymer has 15% by weight of (meth)acrylic acid monomer units based on its weight, the first (meth)acrylate copolymer further comprises monomer units of a “high Tg” monomer, typically 5% by weight or more (in some embodiments, 7.5% by weight or more, 10% by weight or more, 12.5% ​​by weight or more, or 15% by weight or more). The Tg of the homopolymer is measured by differential scanning calorimetry and is often reported in the Polymer Properties Database at polymerdatabase.com. Suitable high-Tg monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-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-Tg monomers have a single vinyl group that is not a (meth)acryloyl group and include various vinyl ethers (e.g., vinyl methyl ether), vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., α-methylstyrene), vinyl halides, and mixtures thereof.In some embodiments, the optionally present second (meth)acrylate copolymer further comprises monomer units of high Tg monomers, including any weight % range described in any embodiment above.

[0091] A first (meth)acrylate copolymer useful in the semi-structural adhesive of the adhesive system of this disclosure contains 0.050% to 5.0% by weight of monomer units of a crosslinkable monomer having two or more (meth)acrylate groups, based on the weight of the (meth)acrylate copolymer. Suitable crosslinkable monomers include diacrylate esters of diols, such as ethylene glycol diacrylate, diethylene glycol diacrylate, propanediol diacrylate, butanediol 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 these diacrylates. Further suitable polyfunctional monomers include polyacrylate esters of polyols, such as glycerol triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, dipentaerythritol pentaacrylate, methacrylates of the acrylates, and combinations thereof. Further suitable polyfunctional crosslinkable monomers include divinylbenzene, allyl methacrylate, diallyl maleate, diallyl phthalate, and combinations thereof. Further suitable polyfunctional crosslinkable monomers include polyacrylate oligomers containing two or more acrylate groups. The polyfunctional acrylate oligomer may be a urethane acrylate oligomer, an epoxy acrylate oligomer, a polyester acrylate, a polyether acrylate, a polyacrylic acrylate, a methacrylate of any of the acrylates, or a combination thereof. Any combination of these crosslinkable monomers may be useful. In some embodiments, in the first (meth)acrylate copolymer, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, or 1.0% by weight or less of monomer units are derived from crosslinkable monomers.In some embodiments, the first (meth)acrylate copolymer contains 0.10% or more by weight, 0.15% or more by weight, 0.20% or more by weight, 0.25% or more by weight, 0.30% or more by weight, 0.40% or more by weight, 0.50% or more by weight, 0.60% or more by weight, or 0.70% or more by weight of monomer units derived from crosslinkable monomers. The second (meth)acrylate copolymer, if present, may contain any of these crosslinkable monomer units in any of the above amounts, or may not contain any crosslinkable monomer units.

[0092] Acrylic polymers are analyzed by nuclear magnetic resonance spectroscopy ( 1 H or 13 ¹

[0093] In some embodiments of the semi-structural adhesives of the adhesive systems of the present disclosure, the first (meth)acrylate copolymer and the second (meth)acrylate copolymer (if present) each independently have a Tg in the range of 2°C to 100°C, 2°C to 80°C, 2°C to 60°C, 2°C to 50°C, 2°C to 45°C, 5°C to 45°C, 5°C to 40°C, 5°C to 35°C, or 10°C to 30°C. In some embodiments, the first (meth)acrylate copolymer and the second (meth)acrylate copolymer (if present) each independently have a Tg of 100°C or less, 80°C or less, 60°C or less, 50°C or less, 45°C or less, or 40°C or less.

[0094] In some embodiments, the semi-structural adhesive of the adhesive system of the present disclosure has a thickness of 0.3 millimeters or more. In some embodiments, the semi-structural adhesive has a thickness of 300 to 6000 micrometers, 300 to 4000 micrometers, 300 to 2000 micrometers, 500 to 2000 micrometers, 800 to 1500 micrometers, or 600 to 1300 micrometers.

[0095] In some embodiments of the semi-structural adhesive tape of the adhesive system of the present disclosure, the semi-structural adhesive comprises 65-99% by weight, 70-95% by weight, 75-95% by weight, 75-90% by weight, or 75-85% by weight of a first (meth)acrylate copolymer, where the weight percentage is based on the total weight of the semi-structural adhesive. In some embodiments, the semi-structural adhesive comprises 1-35% by weight, 1-30% by weight, 2-25% by weight, 3-25% by weight, 3-20% by weight, 4-20% by weight, or 4-15% by weight of a second (meth)acrylate copolymer, where the weight percentage is based on the total weight of the semi-structural adhesive.

[0096] In some embodiments, the semi-structural adhesive of the adhesive system of the present disclosure comprises a further (meth)acrylate copolymer in an amount of 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0% by weight, wherein the further (meth)acrylate copolymer comprises, based on its weight, 0.1% to 15% by weight (in some embodiments, 0.1 to 12% by weight, 0.1 to 11% by weight, 0.1 to 10% by weight, 0.2 to 10% by weight, 0.2 to 9% by weight, 0.2 to 8% by weight, 0.3 to 8% by weight, 0.5 to 8% by weight, 0.5 to 6% by weight, 1 to 6% by weight, or 1 to 5% by weight) of (meth)acrylic acid monomer units. Such further (meth)acrylate copolymers in the adhesive film of the present disclosure may tend to reduce the Tg and / or storage modulus of the semi-structural adhesive and may also tend to reduce the cohesive strength of the semi-structural adhesive.

[0097] The first (meth)acrylate copolymer and the second (meth)acrylate copolymer, useful in some embodiments of the semi-structural adhesives of the adhesive systems of this disclosure, the (meth)acrylate copolymer, useful in the pressure-sensitive adhesives of the adhesive systems of this disclosure, and the polyacrylate, useful in some embodiments of the primer compositions of this disclosure, can each also be prepared by any known radical polymerization method, which includes solution, radiation, bulk, dispersion, emulsion, solvent-free, and suspension processes. The resulting copolymers may be random copolymers or block copolymers. In some embodiments, the first (meth)acrylate copolymer is prepared as a copolymer composition in solution or syrup form.

[0098] Typical solution polymerization is carried out by adding 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 a high temperature (typically about 40–100°C) until the reaction is complete (typically about 1–24 hours, depending on batch size and temperature). Examples of solvents include methanol, tetrahydrofuran, ethanol, isopropanol, tert-butanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and ethylene glycol alkyl ethers. These solvents may be used individually or in mixtures. In typical thermal polymerization, the monomer mixture can be exposed to thermal energy in the presence of a thermal polymerization initiator (i.e., a thermal initiator). An example of a suitable thermal initiator is available from DuPont under the trade name "VAZO".

[0099] The syrup polymer technique involves partially polymerizing monomers to produce a syrup polymer comprising a (meth)acrylate copolymer and unpolymerized monomers. The syrup polymer composition can be polymerized to a useful coating viscosity, applied to a substrate (e.g., tape support material), and further polymerized. In some embodiments, polymerization is carried out in the absence of solvents that do not react with the functional groups of the syrup polymer components, such as ethyl acetate, toluene, or tetrahydrofuran.

[0100] In some embodiments, applicable syrup polymers useful in adhesive tapes of the adhesive systems of the present disclosure are prepared by photoinitiated radical polymerization. Polymerization to obtain applicable viscosity can be carried out such that the monomer-to-polymer conversion rate is up to about 10%. Polymerization can be achieved by exposing the syrup polymer composition to light energy in the presence of a photoinitiator. Polymerization can be stopped by removing the light source and blowing air (oxygen) into the solution to deactivate the growing radicals once the desired conversion rate and viscosity are achieved. In some cases, an energy-activating initiator may not be necessary, for example, when ionizing radiation is used to initiate polymerization.

[0101] In some embodiments, the radical photoinitiators useful for producing adhesive tapes of the adhesive systems of the present disclosure are type I (cleavage-type) photoinitiators. Cleavage-type photoinitiators include acetophenones, α-aminoalkylphenones, benzine ethers, benzoyl oximes, acyl (e.g., benzoyl)phosphine oxides, acyl (e.g., benzoyl)phosphinates, and combinations thereof. Examples of useful benzine ethers include benzine methyl ether and benzine butyl ether. Examples of suitable acetophenone compounds include 4-diethylaminoacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-4'-morpholinobylophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,2-dimethoxyacetophenone, and 2,2-dimethoxy-1,2-diphenylethane-1-one. Examples of suitable acylphosphine oxides, acylphosphinates, and acylphosphonate compounds include bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, dimethylpivaloylphosphonate, and poly(oxy-1,2-ethanediyl)-α,α',α”-1,2,3-propanetriyl Lutris[ω-[[phenyl(2,4,6-trimethylbenzoyl)phosphinyl]oxy]] is one example. Further suitable photoinitiators include substituted α-ketoles such as 2-methyl-2-hydroxypropiophenone, aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride, and photoactive oximes such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Many photoinitiators are available, for example, from BASF (Vandalia, Illinois) under the trade name "IRGACURE," and from IGM Resins (Waalwijk, Netherlands) under the trade names "OMNIRAD" and "ESACURE." Two or more of these photoinitiators can also be used in any combination.Additional photoinitiators can be added to the mixture after the copolymer has been formed (i.e., the photoinitiator can be added to the syrup polymer mixture).

[0102] By measuring the refractive index of the polymerization mixture, the conversion rate (from monomer to copolymer) during irradiation can be monitored.

[0103] If necessary, a chain transfer agent can be added to the monomer mixture to prepare the acrylic copolymers disclosed herein (e.g., polyacrylates in primers, pressure-sensitive adhesives in adhesive tapes, semi-structural adhesives in adhesive tapes). Examples of useful chain transfer agents include carbon tetrabromide, alcohols, mercaptans, and mixtures thereof. In some embodiments, the chain transfer agent comprises at least one of isooctylthioglycolate or carbon tetrabromide.

[0104] The adhesive in the adhesive tape of the adhesive system of this disclosure (e.g., a pressure-sensitive adhesive or a semi-structural adhesive) may optionally include a tackifying resin, particularly a hydrogenated hydrocarbon tackifying resin. Examples of hydrogenated hydrocarbon tackifying resins include C9 and C5 hydrogenated hydrocarbon tackifying resins. Examples of C9 hydrogenated hydrocarbon-based tackifying resins include "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.; and "ARKON P-140", "ARKON P-125", "ARKON P-115", and "ARKON" sold by Arakawa Chemical Inc. (Chicago, Illinois). Examples include "P-100", "ARKON P-90", "ARKON M-135", "ARKON M-115", "ARKON M-100", and "ARKON M-90"; these are trade names of the "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 for the adhesive system of this disclosure is substantially free of tackifiers, particularly hydrocarbon tackifiers.

[0105] The adhesive tapes of the adhesive systems of this disclosure (e.g., pressure-sensitive adhesives or semi-structural adhesives) may contain other additives as needed. For example, they may contain leveling agents, UV absorbers, hindered amine light stabilizers (HALS), oxygen inhibitors, wetting agents, rheology modifiers, defoamers, biocides, flame retardants, and dyes. These additives and their use are known to those skilled in the art and can be used as long as they do not impair the adhesive properties.

[0106] In some advantageous embodiments, adhesives useful in adhesive tapes of adhesive systems of the present disclosure (e.g., semi-structural adhesives or pressure-sensitive adhesives) include filler materials, particularly particulate filler materials. In some embodiments, any filler material used herein includes at least one of polymer microspheres, hollow ceramic microspheres, or glass bubbles.

[0107] In some embodiments, the adhesive useful in the adhesive tape of the adhesive system of the present disclosure (e.g., a semi-structural adhesive or a pressure-sensitive adhesive) takes the form of a foam. The foam contains voids, which may be open cells or closed cells. In some embodiments, the voids are present in the foam in amounts of 5% or more by volume, 10-55% by volume, 10-45% by volume, 15-45% by volume, or 20-45% by volume. The adhesive film in foam form typically has a density of 0.45 g / cm³. 3 ~1.5g / cm 3 0.45 g / cm³ 3 ~1.10g / cm 3 , 0.50 g / cm³ 3 ~0.95g / cm 3 , 0.60 g / cm³ 3 ~0.95g / cm 3 , or 0.70 g / cm³ 3 ~0.95g / cm 3 It has a density of .

[0108] In some embodiments, the adhesive foam useful in the adhesive tape of the adhesive system of the present disclosure has a thickness of 100 to 6000 micrometers, 200 to 4000 micrometers, 500 to 2000 micrometers, or 800 to 1500 micrometers. In some embodiments, the adhesive foam has a thickness of 300 micrometers or more. As will be apparent to those skilled in the art from the description herein, the thickness of the foam adhesive depends on the application.

[0109] Voids or cells in a foam can be formed by any method known in the art, including the use of gases or blowing agents and / or the inclusion of hollow particles in the foam composition. For example, according to the foam-forming method described in U.S. Patent No. 4,415,615 (Esmay et al.), an acrylic foam can be obtained by foaming a composition containing an acrylate monomer and any copolymer monomer, coating the foam onto a support, and polymerizing the foamed composition. Alternatively, a non-foaming composition of an acrylate monomer and any copolymer monomer can be coated onto a support, and the composition can be foamed and polymerized simultaneously. Foaming of the composition can be achieved by stirring in a gas into the polymerizable composition in the presence of a surfactant (e.g., hydrocarbon-based or fluorinated surfactant) or surface-modifying nanoparticles to stabilize the foam. Inert gases, such as nitrogen, argon, and carbon dioxide, may be particularly useful when polymerization is photoinitiated.

[0110] In some embodiments, adhesive forms useful in adhesive tapes of the adhesive systems of the present disclosure incorporate hollow fillers, such as hollow polymer particles, hollow glass microspheres, and hollow ceramic microspheres. Hollow polymer microspheres include, for example, elastomer particles available from Akzo Nobel (Amsterdam, Netherlands) under the trade name "EXPANCEL". Examples of hollow ceramic microspheres include alumina / silica microspheres ("FILLITE", Pluess-Stauffer International) with a particle size of 5 to 300 microns and a specific gravity of 0.7, aluminum silicate microspheres ("Z-LIGHT") with a specific gravity of about 0.45 to about 0.7, calcium carbonate-coated vinylidene fluoride copolymer microspheres ("DUALITE 6001AE", Pierce & Stevens Corp.) with a specific gravity of 0.13, and 3M Company (Saint, Minnesota). Examples include Glass Bubbles sold by Paul, K1, K15, K20, K25, K37, K46, S15, S22, S32, S35, S38, S38HS, S38XHS, S42HS, S42XHS, S60, S60HS, iM30K, iM16K, XLD3000, XLD6000, and G-65 grade "3M Glass Bubbles," as well as any "3M Glass Bubbles" in the HGS series. Foams containing hollow microspheres are called syntactic foams. Foam adhesives may also contain hydrocarbon elastomers, as described in U.S. Patent No. 5,024,880 (Vesley et al.).

[0111] Adhesives useful in adhesive tapes of the adhesive systems of this disclosure may be prepared by simply blending (meth)acrylate copolymers with optional components (e.g., filler materials or tackifying resins). The copolymers can be blended using several conventional methods, such as melt blending, solvent blending, or other suitable physical methods.

[0112] Physical blending equipment that provides dispersion mixing, distribution mixing, or a combination thereof is useful for preparing homogeneous blends. Both batch and continuous physical blending methods are available. Examples of batch methods include the BRABENDER (using the BRABENDER PREP CENTER from CWBrabender Instruments, Inc., South Hackensack, NJ) and the BANBURY internal kneading and roll mill (using equipment from FARREL COMPANY, Ansonia, CT). Examples of continuous methods include single-screw extrusion, twin-screw extrusion, disc extrusion, reciprocating single-screw extrusion, and pin barrel single-screw extrusion. The continuous method may include the use of both dispersion elements, such as cavity transfer elements (e.g., CTM from RAPRA Technology, Ltd., Shrewsbury, England) and pin mixing elements, static mixing elements, and distribution elements (e.g., MADDOCK mixing elements or SAXTON mixing elements ("Mixing in Single-Screw Extruders," Mixing in Polymer Processing, edited by Chris Rauwendaal, Marcel Dekker Inc., New York (1991), pp. 129, 176-177, 185-186)).

[0113] In some embodiments, a semi-structural adhesive useful in an adhesive tape of the adhesive system of the present disclosure contains 65-98% by mass, 70-95% by mass, 75-95% by mass, 75-90% by mass, or 75-85% by mass of a first (meth)acrylate copolymer; 0-35% by mass, 1-35% by mass, 1-30% by mass, 2-25% by mass, 3-25% by mass, 3-20% by mass, 4-20% by mass, or 4-15% by mass of a second (meth)acrylate copolymer; and optionally, 2-15% by mass, 2-14% by mass, or 2-12% by mass of a filler material comprising at least one of polymer microspheres and glass bubbles, where these mass percentages are based on the total mass of the semi-structural adhesive.

[0114] In some embodiments, the second (meth)acrylate copolymer useful in adhesive tapes of the adhesive systems of the present disclosure is prepared using essentially solvent-free radical polymerization, particularly essentially solvent-free thermal radical polymerization. In some embodiments, the second (meth)acrylate copolymer used herein is prepared by essentially adiabatic polymerization. The conversion rate (from monomer to copolymer) can be monitored by measuring the refractive index of the polymerization mixture.

[0115] In some embodiments, a second (meth)acrylate copolymer useful in adhesive tapes of the adhesive system of the present disclosure is obtained as a prepolymer composition having a polymerization conversion rate of more than 10%, more than 15%, more than 20%, more than 25%, more than 30%, more than 35%, more than 40%, or more than 45%, and in some embodiments, the polymerization conversion rate is in the range of 10-60%, 20-55%, 30-50%, or 35-50%.

[0116] According to one aspect of the present disclosure, a semi-structural adhesive useful in an adhesive tape of the adhesive system of the present disclosure may be prepared by incorporating a second (meth)acrylate copolymer into a curable precursor composition of a first (meth)acrylate copolymer, the curable precursor composition of the first (meth)acrylate copolymer comprising a linear or branched alkyl (meth)acrylate monomer, a (meth)acrylic acid monomer, a crosslinked monomer, an optional polymerization initiator, and an optional particulate filler material, thereby forming a curable precursor composition of an adhesive film. The first (meth)acrylate copolymer is formed in a subsequent second step, in which the linear or branched alkyl (meth)acrylate monomer, the (meth)acrylic acid monomer, and the crosslinked monomer are polymerized in the presence of the second (meth)acrylate copolymer to form the first (meth)acrylate copolymer in situ. In some embodiments, the second (meth)acrylate copolymer is diluted in the curable precursor composition of the first (meth)acrylate copolymer and mixed by shaking. In some embodiments, the step of polymerizing linear or branched alkyl (meth)acrylate monomers, (meth)acrylic acid monomers, and crosslinked monomers to form a first (meth)acrylate copolymer is carried out using chemical irradiation in the presence of a second (meth)acrylate copolymer.

[0117] According to another aspect of the present disclosure, the adhesive useful in the adhesive tape in the adhesive system of the present disclosure is a multilayer adhesive laminate comprising the adhesive in the form of a first adhesive layer (in some embodiments, a first adhesive foam layer), and further comprising a second adhesive layer adjacent to the first adhesive film layer. The first adhesive layer and the second adhesive layer may be the pressure-sensitive adhesive described above, the semi-structural adhesive described above, or a combination thereof.

[0118] This type of multilayer adhesive laminate, particularly two-layer or skin-core-skin foam tape laminate, has advantages over single-layer adhesives in that the initial adhesion (immediate bonding strength) can be adjusted by the formulation of the second adhesive layer (also called the skin layer), while the overall properties / requirements of the laminate (e.g., application challenges, deformation behavior, energy dispersion, etc.) can be addressed by the appropriate formulation of the first adhesive film layer (also called the core layer).

[0119] In some embodiments, the multilayer adhesive laminate described herein is a skin / core type multilayer adhesive laminate, where the first layer is a semi-structural adhesive according to any of the embodiments described above, which in some embodiments takes the form of a foam and is the core layer of the multilayer adhesive laminate, and the second adhesive layer is the skin layer of the multilayer adhesive laminate.

[0120] In some embodiments, the multilayer adhesive laminate described herein further includes a third adhesive layer, forming, for example, a three-layer multilayer adhesive laminate. In some embodiments, the third adhesive layer is adjacent to the first adhesive layer and is located on the side of the first adhesive layer opposite to the side adjacent to the second adhesive layer. In some embodiments, the first, second, and third adhesive layers are laminated.

[0121] In some embodiments, the multilayer adhesive assembly is in the form of a skin / core / skin multilayer adhesive assembly, where the first adhesive layer is a semi-structural adhesive in the form of a foam as described in any of the embodiments above 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.

[0122] The second adhesive layer and / or the third adhesive layer may have any composition known in the art. Therefore, the compositions of these various layers used in the multilayer adhesive assemblies of this disclosure are not particularly limited.

[0123] In some embodiments, the second adhesive layer and / or the third adhesive layer comprises a polymer-based material independently selected from the group consisting of polyacrylate, polyurethane, polyolefin, polyamine, polyamide, polyester, polyether, polyisobutylene, polystyrene, polyvinyl, polyvinylpyrrolidone, natural rubber, synthetic rubber, and any combination thereof, copolymers, or mixtures.

[0124] In some embodiments, the second and third adhesive layers independently comprise a pressure-sensitive adhesive (meth)acrylate copolymer or a polyacrylate polymer-based material as described above for semi-structural adhesive compositions. In some embodiments of the multilayer adhesive assemblies of this disclosure, the second and / or third adhesive layers have the same or similar (co)polymer composition as described above for semi-structural adhesives of this disclosure. In some of these embodiments, the second and / or third adhesive layers are filler-free and / or not foamed.

[0125] According to some embodiments of the multilayer adhesive assemblies of the present disclosure, the second adhesive layer and / or third adhesive layer further comprises a tackifying resin, in particular a hydrocarbon tackifying resin. The tackifying resin may be any of those described above. Advantageously, the tackifying resin is selected from the group consisting of C5 hydrocarbon resins, C9 hydrocarbon resins, C5 / C9 hydrocarbon resins, and any combination or mixture thereof or hydrogenated forms.

[0126] In some embodiments of the multilayer adhesive assemblies of this disclosure, the polymerizable material used to produce a second adhesive layer and / or a third adhesive layer is a first / main monomer consisting of 50-99.5% by weight or 60-95% by weight of a linear or branched alkyl (meth)acrylate ester, which in some embodiments is a main monomer selected from the group consisting of isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate, and butyl acrylate. The material comprises optionally 1.0-50% by weight, 3.0-40% by weight, 5.0-35% by weight, or 10-30% by weight of a high Tg monomer as described in any of the above embodiments, optionally 0.1-15% by weight, 0.5-15% by weight, 1.0-10% by weight, 2.0-8.0% by weight, 2.5-6.0% by weight, or 3.0-6.0% by weight of a polar monomer such as a polar (meth)acrylate, and optionally a tackifying resin, the weight percentages of which are based on the total weight of the polymerizable material used to produce the second adhesive layer and / or the third adhesive layer.

[0127] According to an advantageous embodiment of the multilayer adhesive assembly of the present disclosure, the second adhesive layer and / or third adhesive layer comprises a polymer-based material further comprising a chlorinated polyolefin (co)polymer. By incorporating the chlorinated polyolefin (co)polymer into the curable precursor of the second and / or third adhesive layer, the resistance of the resulting adhesive layer to thermal bonding degradation and thermal / humidity bonding degradation can be improved, particularly for low surface energy (LSE) substrates. In some embodiments, the second and / or third adhesive layer does not contain a chlorinated polyolefin (co)polymer.

[0128] Examples of suitable chlorinated polyolefin (co)polymers that may be used in this disclosure include those sold by Eastman Chemical Co. under the trade name "CPO 343-1", "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 Co., and "TYRIN CPE 4211P", "TYRIN CPE 6323A", and "TYRIN CPE 3615P" sold by Dow Chemical Co. Suitable chlorinated polyolefins include chlorinated polypropylene, chlorinated polyethylene, chlorinated ethylene / vinyl acetate copolymers, and any combination, mixture, or copolymer thereof. In some embodiments, the chlorinated polyolefin (co)polymer is chlorinated polypropylene.

[0129] In some embodiments, the multilayer adhesive assemblies described in any of the embodiments above are obtained by a wet-on-wet coating process step. Representative "wet-in-wet" manufacturing processes that may be used here are described, for example, in International Patent Application Publication WO-A1-2011094385 (Hitschmann et al.) or European Patent Application Publication EP-A1-0259094 (Zimmerman et al.). In some embodiments, the method for manufacturing the multilayer adhesive assembly includes a wet-on-wet coating process step.

[0130] In another aspect, the disclosure relates to a process for manufacturing a multilayer adhesive assembly as described in any of the above embodiments, the process comprising stacking a (liquid) precursor of a first adhesive layer, a (liquid) precursor of a second adhesive layer, and an optional third adhesive layer (liquid) precursor to form a curable precursor of a multilayer adhesive assembly, and curing the curable precursor of the multilayer adhesive assembly, the curing of which is performed using a chemical beam in some embodiments.

[0131] In some embodiments of the manufacturing process for multilayer adhesive assemblies, the (lower) layer of the curable (liquid) precursor of a second adhesive layer is covered by the (upper) layer of the curable (liquid) precursor of an adjacent first adhesive layer, with substantially no exposure of the (lower) layer of the curable (liquid) precursor of the second adhesive layer.

[0132] In some embodiments, multilayer adhesive assemblies are manufactured by a continuous and self-metered process for producing multilayer adhesive assemblies. In some of these embodiments, the process includes providing two or more coating knives, independently, offset from each other and from the substrate, to form gaps normal to the surface of the substrate; moving the substrate downstream of the coating knives; and supplying a curable (liquid) precursor for a first adhesive layer, a curable (liquid) precursor for a second adhesive layer, and an optional third adhesive layer upstream of the coating knives, thereby coating the substrate with two or more curable liquid precursors as superimposed layers through their respective gaps. In light of the disclosure herein and U.S. Patent Application Publication No. 2013 / 0004694 (Hitschmann et al.), suitable setup and configuration of coating apparatus, coating knives and coating stations, in particular, for carrying out the continuous and self-metered method for producing multilayer adhesive assemblies as described above, is within the capabilities of those skilled in the art.

[0133] In some embodiments of the manufacturing process for multilayer adhesive assemblies, a first adhesive layer, a second adhesive layer, and an optional third adhesive layer are prepared individually and then laminated together. In another embodiment of the manufacturing process for multilayer adhesive assemblies, the process includes a (co)extrusion step. In yet another embodiment of the manufacturing process for multilayer adhesive assemblies, the process is as described in U.S. Patent No. 4,818,610 (Zimmerman et al.), which includes the step of sequentially coating a substrate with liquid compositions, each containing at least one photopolymerizable monomer. A liner can be attached to the top layer, and the multiple overlapping layers are cured by irradiation to provide an adhesive tape.

[0134] The adhesive film, comprising a pressure-sensitive adhesive or semi-structural adhesive as described in any of the above embodiments, can be conveniently coated on or between liners, and the liners may be treated with a release coating. Any suitable material can be used for the liners and the release coating. In some embodiments, the adhesive film is coated on a liner having different release properties on both sides and is sometimes wound into a roll.

[0135] The primers and adhesive tapes of the adhesive systems of this disclosure can be applied to a variety of substrates, as described in any embodiment above. The substrates may be flexible or rigid and may be formed from polymer materials, glass or ceramic materials, metals, or combinations thereof. Suitable polymer substrates include polymer films made from polypropylene, polyethylene, polyvinyl chloride, polyester (polyethylene terephthalate or polyethylene naphthalate), polycarbonate, polymethyl (meth)acrylate (PMMA), cellulose acetate, triacetylcellulose, and ethylcellulose. Foam substrates may also be used. Other examples of substrates include stainless steel, polymer materials coated with metal or metal oxides, and glass coated with metal or metal oxides.

[0136] In this disclosure, the term "low surface energy substrate" means a substrate having a surface energy of less than 34 dynes per centimeter. The term "medium surface energy substrate" means a substrate having a surface energy in the range of 34 to 70 dynes per centimeter, typically 34 to 60 dynes per centimeter, and more typically 34 to 50 dynes per centimeter. The term "high surface energy substrate" means a substrate having a surface energy greater than 350 dynes per centimeter, typically greater than 400 dynes per centimeter, and more typically in the range of 400 to 1100 dynes per centimeter. Surface energy is typically determined from contact angle measurements, such as those described in ASTM D7490-08.

[0137] The adhesive films and multilayer adhesive assemblies of this disclosure may be useful for forming strong adhesive bonds to low surface energy (LSE) substrates. Such materials include polypropylene, polyethylene (e.g., high-density polyethylene or HDPE), polypropylene blends (e.g., PP / EPDM, TPO), or certain clear coat surfaces. Other substrates may also have low surface energy properties due to the presence of residues such as oil residue or films such as coatings on the substrate surface.

[0138] The adhesive films and multilayer adhesive assemblies of this disclosure may also be useful for bonding to medium surface energy (MSE) substrates, such as polyamide 6 (PA6), acrylonitrile butadiene styrene (ABS), polycarbonate (PC) / ABS blends, PC, PVC, polyurethane (PUR), thermoplastic elastomer (TPE), polyoxymethylene (POM), polystyrene, poly(methyl methacrylate) (PMMA), certain clear coat surfaces, particularly clear coats on vehicles such as cars, or coating surfaces for industrial applications, and composite materials such as fiber-reinforced plastics.

[0139] The adhesive films and multilayer adhesive assemblies of this disclosure may also be useful for bonding to high surface energy (HSE) substrates, such as ceramics, glass, and metals.

[0140] Accordingly, this disclosure is further directed toward the use of the adhesive systems described above in bonding to low surface energy substrates, medium surface energy substrates and / or high surface energy substrates.

[0141] The adhesive systems of this disclosure can be used in any article that typically uses such assemblies, such as labels, tapes, signs, covers, marking indexes, display components, and touch panels.

[0142] A method for manufacturing a bonded article may include the steps of applying a primer composition to the surface of a first substrate, and then applying an adhesive tape to the primer composition on the surface of the first substrate. Before applying the adhesive tape, the primer composition may be left on the substrate for 5 minutes or more, 10 minutes or more, 15 minutes or more, 30 minutes or more, or 60 minutes or more. In some embodiments, the adhesive tape is a double-sided tape. In some embodiments, the method further includes the steps of applying a primer composition to the surface of a second substrate, and then applying an adhesive tape to the primer composition on the surface of the second substrate, thereby bonding 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.

[0143] The primer composition and adhesive tape in the adhesive system of this disclosure can be coated / applied to a substrate using any conventional coating technique that has been appropriately modified to suit a particular substrate. For example, the primer composition can be applied / coated to various solid substrates by methods such as roller coating, flow coating, dip coating, spin coating, spray coating, knife coating, and die coating. These various coating methods allow the primer composition to be placed on the substrate at various thicknesses, thereby expanding the range of applications for the adhesive system.

[0144] The substrates to which the primer compositions and adhesive tapes of this disclosure can be applied are selected according to the specific application. For example, the primer compositions and adhesive tapes may be applied to sheet products (e.g., decorative graphics and reflective products), label stocks, and tape supports. Furthermore, the adhesive films and multilayer adhesive assemblies of this disclosure can be applied directly to other substrates, such as metal panels (e.g., automotive panels) or glass windows, thereby enabling the attachment of other substrates or objects to those panels or windows. Thus, the adhesive films and multilayer adhesive assemblies of this disclosure may find specific applications in the automotive manufacturing industry (e.g., for attaching exterior trim parts and weatherstripping), the construction industry, or the solar panel construction industry.

[0145] Accordingly, this disclosure further relates to industrial applications of the adhesive systems of this disclosure, particularly in construction applications, automotive applications (including special vehicles such as trucks, trains, and buses), home appliances, coatings, and displays.

[0146] As described above, adhesive tapes generally adhere to a primer-treated substrate surface when applied without the use of heat or radiation. Adhesive tapes generally adhere to a primer-treated substrate surface without forming covalent bonds. Advantageously, adhesive tapes do not require crosslinking agents or reactive chemical species to build adhesive strength. Therefore, adhesive tapes generally do not contain thermosetting crosslinking additives such as polyfunctional aziridines, isocyanates, or epoxys, or chemical crosslinking agents such as peroxides. Adhesive tapes also generally do not contain photochemical crosslinking additives that are activated after application to the substrate. In some embodiments, the adhesive tapes of this disclosure do not contain polyfunctional aziridines, polyfunctional isocyanates, polyfunctional epoxides, benzophenones, triazines, polyfunctional carboxylates, oxetanes, or oxazolines.

[0147] As shown in the following embodiments, the adhesive systems of the present disclosure provide excellent adhesion to a variety of substrates, and in embodiments of semi-structural tapes, they exhibit cohesive failure or adhesive failure of at least 50 N / cm of the adhesive tape. The cohesive failure of the pressure-sensitive adhesive tapes shown in Examples 19-30 indicates that adhesion to the primer is stronger than the cohesive force within the tape. In some embodiments, the use of a solvent in the primer composition improves adhesion, particularly to MSE or LSE substrates. See, for example, the comparison between Example 9 and Example 10, or between Example 11 and Example 12. Although the present disclosure is not bound by theory, it is thought that the solvent reduces the surface tension of the primer composition, thereby improving wettability on MSE or LSE surfaces. It may also help in the film formation of the polymer in the primer composition.

[0148] Some embodiments of this disclosure In a first embodiment, the Disclosure provides a primer composition comprising a polyacrylate dissolved or dispersed in water, wherein the polyacrylate comprises, based on the total weight of monomer units in the polyacrylate, at least 20% by weight of methyl methacrylate units, at least 15% by weight of monomer units comprising at least one of secondary amines, tertiary amines or tertiary amides, at least 15% by weight of acrylic monomer units comprising alkyl groups having at least 4 carbon atoms, and 2.5 to 10% by weight of acrylic monomer units comprising carboxylic acid groups. In a second embodiment, the disclosure provides a primer composition of the first embodiment, wherein the monomer unit comprising at least one of a secondary amine, a tertiary amine, or a tertiary amide comprises at least one of 2-(N,N-dimethylaminoethyl)(meth)acrylate, 2-(N,N-diethylaminoethyl)(meth)acrylate, 2-(t-butylaminoethyl)(meth)acrylate, 2-(N,N-dimethylaminoethyl)(meth)acrylamide, 2-(N,N-diethylaminoethyl)(meth)acrylamide, 2-(t-butylaminoethyl)(meth)acrylamide, N-(meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidone. In a third embodiment, the disclosure provides a primer composition of the first or second embodiment in which methyl methacrylate units, monomer units comprising at least one of secondary amines, tertiary amines, or tertiary amides, acrylic monomer units comprising an alkyl group having at least four carbon atoms, and acrylic monomer units comprising a carboxylic acid group together constitute at least 95% by weight of the monomer units in a polyacrylate. In a fourth embodiment, the disclosure provides a primer composition according to any of the first to third embodiments, wherein, based on the total weight of monomer units in the polyacrylate, methyl methacrylate units are present in an amount of 25 to 65% by weight, monomer units comprising at least one of secondary amines, tertiary amines, or tertiary amides are present in an amount of 15 to 40% by weight, acrylic monomer units comprising an alkyl group having at least four carbon atoms are present in an amount of 15 to 40% by weight, and acrylic monomer units comprising a carboxylic acid group are present in an amount of 3 to 7% by weight. In a fifth embodiment, the disclosure provides a primer composition of any of the first to fourth embodiments, further comprising at least one of a humidity stabilizer, an adhesion promoter, or a wetting agent. In a sixth embodiment, the disclosure provides a primer composition of any of the first to fifth embodiments, further comprising a polyamide. In a seventh embodiment, the disclosure provides a primer composition of the sixth embodiment comprising a polyamide, a further diamine comprising at least one of a dimer acid, an oxyalkylenediamine, a primary diamine, or a secondary diamine, and a sulfonic acid-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic acid ester, or a diamine. In an eighth embodiment, the disclosure provides a primer composition of the seventh embodiment in which the mole fraction of a dimer acid is 0.40 to 0.99, the mole fraction of a sulfonic acid-functional monomer is 0.01 to 0.20, and the mole fraction of at least one second diacid is 0 to 0.60, these based on the total number of moles of a combination of a dimer acid, at least one second diacid, and a sulfonic acid-functional dicarboxylic acid or dicarboxylic acid ester, and the mole fraction of oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of at least one second diamine is 0.90 to 0.995, these based on the total number of moles of a combination of oxyalkylenediamine, further diamine, and a sulfonic acid-functional diamine. In the ninth embodiment, the disclosure provides a primer composition of any of the first to eighth embodiments, further comprising a solvent. In a tenth embodiment, the disclosure provides a primer composition of the ninth embodiment in which the solvent comprises at least one of propylene carbonate, alcohol, polyol, polyol ether, polyol ether ester, or dibasic acid ester. In an eleventh embodiment, the disclosure provides a primer composition of the tenth embodiment in which the solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester. In a twelfth embodiment, the disclosure provides the use of any of the primer compositions of the first to tenth embodiments as a primer for adhesive tapes.

[0149] In a thirteenth embodiment, the disclosure provides a primer composition comprising a polymer dispersed in water and a solvent, wherein water accounts for at least 50% by weight of the primer composition. In a fourteenth embodiment, the disclosure provides a primer composition of the thirteenth embodiment, wherein the solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester. In the fifteenth embodiment, the disclosure provides a primer composition of the tenth, eleventh, thirteenth, or fourteenth embodiment, wherein the solvent accounts for 2% or more and 25% or less by weight of the primer composition. In a sixteenth embodiment, the disclosure provides a primer composition of the thirteenth, fourteenth, or fifteenth embodiment, wherein the primer composition comprises at least one of polyamides, polyurethanes, or polyacrylates, or at least one of polyamides or polyacrylates. In the 17th embodiment, the disclosure provides a primer composition of the 16th embodiment, wherein the primer composition comprises a polyacrylate of any of the 1st to 4th embodiments. In the 18th embodiment, the disclosure provides a primer composition of any of the 13th to 17th embodiments, wherein the primer composition comprises a polyamide. In the 19th embodiment, the disclosure provides a primer composition of the 18th embodiment, comprising a polyamide, a further diamine comprising at least one of a dimer acid, an oxyalkylenediamine, a primary diamine, or a secondary diamine, and a sulfonic acid-functional monomer comprising at least one of a dicarboxylic acid, a dicarboxylic acid ester, or a diamine. In the 20th embodiment, the disclosure provides a primer composition of the 19th embodiment based on the total number of moles of the combination of oxyalkylenediamine, further diamine, and sulfonic acid-functional diamine, respectively, wherein the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the sulfonic acid-functional monomer is 0.01 to 0.20, the mole fraction of at least one second diacid is 0 to 0.60, the mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of at least one second diamine is 0.90 to 0.995. In the 21st embodiment, the disclosure provides a primer composition of any of the 13th to 20th embodiments, further comprising at least one of a humidity stabilizer, an adhesion promoter, or a wetting agent. In the 22nd embodiment, the disclosure provides the use of any of the primer compositions of the 13th to 21st embodiments as a primer for adhesive tapes.

[0150] In the 23rd embodiment, the disclosure provides an adhesive system comprising a primer composition and an adhesive tape of any of the 1st to 11th or 13th to 21st embodiments. In a 24th embodiment, the disclosure provides an adhesive system of the 23rd embodiment in which the primer composition is not a component of the adhesive tape. In a 25th embodiment, the disclosure provides an adhesive system of a 23rd or 24th embodiment in which the adhesive tape comprises at least one of an acrylic adhesive or a rubber-based adhesive. In the 26th embodiment, the disclosure provides an adhesive system according to any of the 23rd to 25th embodiments, wherein the adhesive tape is a pressure-sensitive adhesive tape. In the 27th embodiment, the disclosure provides an adhesive system of any of the 23rd to 25th embodiments, wherein the adhesive tape is a semi-structural adhesive tape. In the 28th embodiment, the disclosure relates that the semi-structural tape includes an adhesive film, and the adhesive film is Based on the weight of the (meth)acrylate copolymer, at least 55% by weight of linear or branched alkyl (meth)acrylate monomer units, Based on the weight of the (meth)acrylate copolymer, 15 to 40% by weight of (meth)acrylic acid monomer units; however, if the (meth)acrylate copolymer contains 15% by weight of (meth)acrylic acid monomer units, the (meth)acrylate copolymer contains at least 5% by weight of high Tg monomer monomer units, based on the weight of the (meth)acrylate copolymer, which provides a homopolymer having a glass transition temperature of 50°C or higher when homopolymerized. and monomer units of crosslinked monomers having 2 or more (meth)acrylate groups, based on the weight of the (meth)acrylate copolymer, in an amount of 0.10 to 5% by weight. The present invention provides an adhesive system of a 27th embodiment, which includes an adhesive film containing [the specified element]. In a 29th embodiment, the disclosure provides an adhesive system of the 28th embodiment, wherein the first (meth)acrylate copolymer comprises 17-20% by weight, or 17-19.5% by weight of (meth)acrylic acid monomer units. In the 30th embodiment, the Disclosure provides an adhesive system of the 28th or 29th embodiment in which the first (meth)acrylate copolymer comprises monomer units of two or more crosslinked monomers having two or more (meth)acrylate groups in an amount of 0.15% by weight or more, 0.20% by weight or more, 0.25% by weight or more, 0.30% by weight or more, 0.40% by weight or more, 0.50% by weight or more, 0.60% by weight or more, or 0.70% by weight or more, based on the weight of the first (meth)acrylate copolymer. In the 31st embodiment, the Disclosure provides an adhesive system of any of the 28th to 30th embodiments, wherein the adhesive film comprises 5% by weight or less of another (meth)acrylate copolymer, which comprises 0.1 to 15% by weight of (meth)acrylic acid monomer units based on the weight of the (meth)acrylate copolymer. In the 32nd embodiment, the disclosure provides an adhesive system of any of the 23rd to 31st embodiments, wherein the adhesive tape or adhesive film includes a foam. In the 33rd embodiment, the disclosure provides an adhesive system of any of the 28th to 32nd embodiments, in which the semi-structural adhesive tape is a multilayer adhesive assembly comprising a first layer of a first (meth)acrylate copolymer and a second adhesive layer adjacent to the first layer. In the 34th embodiment, the disclosure provides an adhesive system of the 33rd embodiment in which the first layer of a first (meth)acrylate copolymer is the core of a skin-core-skin multilayer adhesive. In the 35th embodiment, the Disclosure provides an adhesive system of any of the 28th to 34th embodiments, wherein the adhesive film comprises a second (meth)acrylate copolymer, the second (meth)acrylate copolymer comprising more than 15% to 40% by weight of (meth)acrylic acid monomer units based on the weight of the second (meth)acrylate copolymer. In the 36th embodiment, the disclosure provides an adhesive system of the 35th embodiment, in which a first (meth)acrylate copolymer is present in a range of 65 to 99% by weight and a second (meth)acrylate copolymer is present in a range of 1 to 35% by weight, based on the total weight of the adhesive film. In the 37th embodiment, the disclosure provides an adhesive system of any of the 23rd to 36th embodiments in which the adhesive tape does not react with the primer composition to form a covalent bond.

[0151] In the 37th embodiment, the Disclosure provides a method for manufacturing a bonded article, the method comprising applying a primer composition of any of the 1st to 11th or 13th to 21st embodiments to the surface of a first substrate, and applying a semi-structural tape to the primer composition on the surface of the first substrate. In a 38th embodiment, the Disclosure provides a method of the 37th embodiment in which the semi-structural tape is a double-sided tape, and the method further comprises applying a primer composition to the 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 the 39th embodiment, the disclosure provides a method of the 37th or 38th embodiment in which the semi-structural tape does not react with the primer composition to form a covalent bond.

[0152] The purposes and benefits of this disclosure are further illustrated by the following non-limiting embodiments. However, the specific materials and their quantities described in these embodiments, as well as other conditions and details, should not be construed as unduly limiting this disclosure. [Examples]

[0153] Unless otherwise specified, all parts, percentages, ratios, etc., in the examples and the remainder of the specification are based on weight. The following abbreviations are used in this section: in = inch, g = gram, pph = percentage, wt = weight%, kg = kilogram, μg = microgram, lb = pound, kN = kilonewton, N = Newton, lbf = pound force, h = hour, min = minute, s = second, °C = degrees Celsius, °F = degrees Fahrenheit, rH = relative humidity, Hz = Hertz, mW = milliwatt, J = joule, ° = angle, m = meter, cm = centimeter, mm = millimeter, μm = micrometer, MPa = megapascal, psi = pounds per square inch, and U / min = times per minute. [Table 1-1] [Table 1-2]

[0154] Test substrate The adhesive tape compositions and assemblies according to this disclosure were tested for adhesive tape properties on the following substrates.

[0155] The stainless steel (SS) sheet ("Edelstahl 1.4301 IIID," 150mm x 50mm x 2mm) was obtained from Rocholl GmbH in Eschenbronn, Germany.

[0156] Aluminum (Al) sheets (150mm x 25mm x 2mm), acrylonitrile butadiene styrene (ABS) sheets (Metzoplast ABS / G, 150mm x 25mm x 2mm), carbon fiber reinforced plastic (CRP) sheets (150mm x 25mm x 2mm), glass sheets (150mm x 25mm x 2mm), polycarbonate sheets (150mm x 25mm x 2mm), powder-coated steel sheets with epoxy powder coating (Powdercoat) (150mm x 25mm x 2mm), polymethyl methacrylate (PMMA) sheets (150mm x 25mm x 2mm), and polystyrene sheets (150mm x 25mm x 2mm) were all obtained from Rocholl GmbH in Aglatershausen, Germany.

[0157] The polypropylene (PP) sheets (150mm x 25mm x 2mm) were obtained from Aquarius Plastics Ltd in Guildford, Surrey, UK.

[0158] Before testing, the substrates were cleaned as follows: Al and SS plates were first cleaned with methyl ethyl ketone (MEK) and n-heptane, dried with tissue, then cleaned with MEK and dried with tissue. Powder-coated plates, CRP plates, glass plates, polycarbonate plates, polystyrene plates, PMMA plates, and ABS panels were lightly wiped with a dry tissue to remove surface residue / waxy compounds, then cleaned with a mixture of isopropyl alcohol / distilled water (1:1), and dried with tissue. PP plates were cleaned with a dry towel only.

[0159] Priming procedure: The test substrate was primed as follows: The primer was dropped onto the edge of a paper towel using a pipette until the primer soaked into the paper towel, moistening the edge of the towel, but no excess primer was visible on the towel surface. The substrate was then wiped with the moistened edge of the paper towel to form a thin, uniform primer layer. Next, the primed substrate was dried in air at 23°C and 50% rH for at least 5 minutes. When applied using this method, the dry coating weight of the primer was 0.1–1 μg / μm². 2 (density 1g / cm³) 3 Assuming this, the layer thickness will be 0.1 to 1 μm.

[0160] [Test method:] 90° peel test at 300 mm / min (according to test method Finat No. 2): The adhesive tape compositions and assemblies strips according to this disclosure were 10 mm wide and more than 175 mm long, and were cut from the sample material along the machine direction. In preparing the test specimens, the liner was first removed from one adhesive side and placed on an aluminum strip measuring 22 × 1.6 cm. Then, the adhesive side of each adhesive tape strip was placed on a primer-treated test panel with the adhesive side facing down, using light pressure after removing the liner. Next, to obtain adhesion between the adhesive and the surface, the test samples were rolled twice in each direction at a speed of approximately 10 mm per second using a standard FINAT test roller (weighing 6.8 kg). After applying the adhesive compositions and assemblies strips to the test panel, the test samples were left at room temperature (23°C ± 2°C, relative humidity 50% ± 5%) for 24 or 72 hours before testing.

[0161] In the peel test, the test sample was first fixed to the movable chuck at the bottom of a Zwick tensile testing machine (model Z020, Zwick / Roell GmbH, Ulm, Germany). The adhesive film strip was folded back at a 90° angle, and its free end was held in the upper chuck of the tensile testing machine in the configuration commonly used for 90° peel measurements. The tensile testing machine was set to a chuck separation speed of 300 mm / min. The test results were expressed in Newtons / 10 mm (N / 10 mm). The recorded peel value was the average of two 90° peel measurements.

[0162] Static shear force test at 110℃ and 750g (FINAT Test Method No. 8, 8th edition, 2009) Static shear force was used to measure the cohesiveness or internal strength of the adhesive. This was measured in minutes, the time required to separate a standard area of ​​the adhesive sheet material from the test panel under stress from a constant standard load.

[0163] A 25mm wide, 12.7mm long strip was cut from a cured adhesive sample along the machine direction. One release liner was removed from the strip, and the exposed adhesive surface was attached to an anodized aluminum support. Then, the second release liner was removed, and the adhesive tape sample was attached to a primer-treated test substrate, providing an adhesive area of ​​25mm × 12.7mm, using light finger pressure. To obtain adhesion between the adhesive layer and the substrate surface, a standard FINAT test roller (6.8kg) was rolled once in each direction at a speed of approximately 10mm / second. After applying the adhesive tape strip to the test panel, it was left at room temperature of 23°C for 24 hours before testing. A loop was formed at the end of the test strip to hold the specified load. The test panel was placed in a shear holding device. After holding at a test temperature of 110°C for 15 minutes, a load of 750g was attached to the loop and the timer was started. Results were recorded in minutes and were the average of three shear measurements. The recorded time of "10000+" indicates that the adhesive did not break even after 10,000 minutes.

[0164] Simple overlap shear test (overlap shear test) based on ASTM D 1002 / DIN EN 1465 Overlap shear (OLS) was used to measure the cohesiveness or internal strength of the adhesive. The aluminum substrate was supplied by Rocholl GmbH (Eschelbronn, Germany), measuring 1 inch × 2 inches × 0.064 inches (2.5 cm × 5 cm × 1.1 mm), and after cleaning with MEK, it was grit sandblasted, cleaned again with MEK, and air-dried for 10 minutes. The substrate was then primed. Priming was performed using a paper towel supplied by 3M, applying it to an area of ​​approximately 2 inches. The primed substrate was air-dried for at least 10 minutes before adhesive application. Test specimens were prepared by cutting 1-inch (2 cm) wide strips of adhesive. First, one liner was removed, and the adhesive was placed along the primed area. A 2-inch (5.1 cm) hard rubber roller was used to ensure complete adhesion of the adhesive. Next, the upper release liner was removed to expose the bonding surface, which was then introduced to the second primed substrate to form a bond. A pressure of approximately 150 N was applied to the closed joint for 30 seconds, and then the specimens were kept at room temperature (23°C ± 2°C, relative humidity 50% ± 5%) for 3 days prior to the test. The dynamic overlap shear test was performed at 23°C using a Zwick tensile testing machine (model Z020, manufactured by Zwick / Roell GmbH). The specimen was mounted on the grip, and the crosshead was operated at a speed of 1 inch / min, applying load until fracture. The stress at fracture was recorded in MPa using the test method disclosed in ASTM D1002.

[0165] Shear storage modulus A strain-controlled rheometer with a vibrational shear mode at a constant frequency of 1 Hz was used, along with a parallel plate geometry (8 mm) (model ARES G2, TA Instruments, 159 Lukens Drive, New Castle, DE 19720, USA). Circular die-cut samples with a diameter of 8 mm and a thickness of 0.6 mm were heated in a temperature range of -50 to +150 °C at a heating rate of 5 °C / min. Vibrational strain and normal force control were adjusted throughout the entire temperature range to maintain proper contact between the sample and the measurement geometry, and to maintain the deformation level within the linear viscoelastic region of the sample material. The glass transition was determined as the peak temperature of the loss tangent. Complex modulus, storage modulus, and loss tangent were monitored throughout the temperature range, specifically measured at 25 °C. Complex modulus was evaluated for comparison of tape formulations. The complex modulus was determined based on the storage modulus and the corresponding loss tangent tanδ, which is the ratio of the loss modulus to the storage modulus, reflecting the Dalquist criterion.

[0166] Preparation examples FL-1 and SL-1 The precursors of the adhesive composition (foam layer and skin layer, hereinafter referred to as FL-1 and SL-1) were prepared in a glass container by combining a monomer composition containing C8 acrylate (2-EHA) and acrylic acid with PI1 at 0.04 pph. Before initiating UV irradiation, the mixture was purged with nitrogen for 10 minutes, and nitrogen was continuously bubbling into the mixture until air was added to the syrup-like mixture and the polymerization process was stopped. The mixture was continuously stirred with a propeller stirrer (300 U / min), and the reaction was stopped when the viscosity, measured with a Brookfield viscometer (type, city, state or country), T=25°C, spindle 4.12 rpm, reached 2800-4000 mPas. Subsequently, the photoinitiator PI1, HDDA and HDDMA crosslinking agents, and fumed silica (FS) particles were added and mixed again. In the third step, microspheres and black pigment were added and mixed with a propeller stirrer (300 U / min) for 5 minutes until they dissolved / dispersed. The precise formulation of the polymerization precursor composition for the first adhesive polymer layer is shown in Table 2 below.

[0167] Preparation of acrylate copolymers: The (meth)acrylate copolymer (hereinafter referred to as Copolymer 2) was prepared as follows. Polymerization was carried out using a Buechi Polycave stainless steel reactor (available from Buechi Labortechnik GmbH, City, The Netherlands). As the first step of polymerization, 250 g of a mixture of EHA (80 wt%), AA (20 wt%), IOTG (0.04 wt%), and 3 ppm of “VAZO52” initiator was charged into the Buechi reactor. The reactor was sealed, oxygen was purged, and it was maintained under a nitrogen pressure of approximately 1 bar. The reaction mixture was heated to 60°C, and the reaction proceeded adiabatically. The peak temperature of the reaction was 110°C. After the reaction was complete, the mixture was cooled to below 50°C. The polymerization conversion rate was approximately 35%.

[0168] Preparation example FL-2: The precursor composition for FL-2 was first prepared by diluting copolymer 2 described above in a polymerization precursor composition containing C8 acrylate (EHA) and AA as described in Table 2. The resulting composition was mixed for approximately 24 hours by shaking in a roll bench (model LD209, available at Labortechnik Froebel, Germany) with a propeller stirrer (150 U / min), and mixing was stopped when a homogeneous and clear mixture was obtained. Next, the photoinitiator PI1, HDDA crosslinker, and FS particles were added and mixed again by shaking for approximately 24 hours. In the third step, glass bubbles (GB) were added and dispersed by stirring for 5 minutes with a propeller stirrer (300 U / min). [Table 2]

[0169] Preparation of semi-structural adhesive tapes 1 and 2: Semi-structural adhesive tape 1 was prepared by alternately laminating the precursor of the adhesive layer skin SL-1 and the precursor of the first adhesive polymer foam core layer FL-1 in a lab coater, according to the method described in International Patent Application Publication No. WO-A1-2011094385 (Hitschmann et al.). Here, the liquid precursor of the skin layer adhesive (e.g., SL-1) was coated on the top and bottom of the adhesive polymer foam core layer FL-1. The knife height settings were 120 μm for the first and third knives (for the adhesive skin layer SL-1) and 620-640 μm for the second knife (for the polymer foam core layer FL-1), all calculated as levels from the substrate surface. Semi-structural adhesive tape 2 was prepared similarly, except that the skin layer was not laminated on the FL-2 polymer foam core layer. Curing was performed from both the top and bottom surfaces in a 600 cm long UV curing station at a line speed of 1.30 m / min. The cumulative total irradiation intensity from the top and bottom surfaces is approximately 4 mW / cm². 2 The semi-structural adhesive tape 1 included a foam core layer FL-1 and two SL-1 skin layers, while the semi-structural adhesive tape 2 included a foam core layer FL-2.

[0170] Preparation of polyamides: All the raw materials listed in Table 3 were added to a 1 L glass flask equipped with a mechanical stirrer, thermocouple, distillation head with a 100 mL receiving flask, and nitrogen gas introduction / exhaust lines. The contents of the flask were heated to 150°C under a nitrogen atmosphere with stirring using an electric mantle and controller. After refluxing the reaction mixture for 60 minutes, the cold finger of the reaction condenser was switched to distillation. When the rate of water generation decreased, the batch temperature was raised to 225°C and held overnight under nitrogen with stirring. 100 ppm of 85% phosphoric acid was added, and a vacuum of 20–30 mmHg was introduced into the flask over 5–10 minutes, maintained for 2 hours, and then the vacuum was released with nitrogen gas. The contents of the flask were poured into an aluminum tray lined with silicone release paper. The contents were collected after being allowed to cool naturally to room temperature. Typical yields were 500 g–700 g. The composition (mol%) of PA1 was PRIPOL 1013: 33%, sebacic acid: 13.5%, DMSSIP: 3.5%, piperazine: 29.25%, ethylenediamine: 17.5%, aminoethylpiperazine: 2.5%, and JEFFAMINE ED-2003: 0.75%. [Table 3]

[0171] Preparation of polyamide dispersions: 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 with a 500 mL receiver flask, according to Table 4. The mixture was heated to 84°C and stirred under a nitrogen atmosphere for 2 hours to form a homogeneous solution. The isopropanol was then removed by distillation under atmospheric pressure to obtain a milky dispersion. The contents of the flask were allowed to cool naturally to room temperature and collected. The solids content in water of each sample was measured by an evaporation test at 105°C for 1 hour. [Table 4]

[0172] Preparation of polyacrylates: Polymer 2 was prepared by solution polymerization. A 45.5% by weight solution was prepared by mixing 2 g of AA, 10.5 g of 2-EHA, 27.5 g of MMA, and 10 g of DMAEMA with 59.6 g of DPGMME in a glass reactor. The mixture was degassed with nitrogen for 1 minute and heated to 65°C. At that temperature, 0.4 g of the "VAZO67" initiator was added, and the mixture was reacted with stirring for 24 hours. After the reaction, 90 g of DPGMME was added to the reactor to further dilute the polymer solution to a solids content of 25%. To obtain the final aqueous polymer solution, 26 g of the diluted polymer was mixed with 50 g of DI water and 1 g of acetic acid for 30 minutes.

[0173] Polymer 3 was prepared by solution polymerization. A 37 wt% solution in DPGMME was prepared by mixing 3 g of AA, 19 g of 2-EHA, 13 g of MMA, and 15 g of 1-vinyl-2-pyrrolizinone with 85 g of DPGMME in a glass reactor. The mixture was degassed with nitrogen for 1 minute and heated to 62°C. At that temperature, 0.05 g of the "VAZO67" initiator was added, and the mixture was reacted with stirring for 24 hours. To obtain the final aqueous polymer solution, 8.78 g of the polymer solution was mixed with 25 g of DI water and 0.5 g of 32% ammonia solution for 30 minutes. Polymer 5 was prepared similarly, except that the amounts of starting materials shown in Table 5 below were used.

[0174] Polymer 4 was produced by emulsion polymerization. A 29% by weight emulsion in water was prepared by mixing 0.8 g of AA, 4.2 g of 2-EHA, 11 g of MMA, and 4 g of DMAEMA with 52.4 g of DI water and a surfactant mix ("TERGITOL 15-S-30" 0.30 g, "TERGITOL TMN-6" 0.60 g, "ETHOQUAD C-12" 0.26 g). The mixture was degassed with nitrogen for 1 minute and heated to 70°C. At that temperature, 0.10 g of "VAZO V50" initiator was added and the mixture was reacted with stirring for 24 hours. The wt% of the starting materials used in polymer dispersions (PDs) 2-5 prepared from polymers 2-5 and their final concentrations in water are shown in Table 5 below. [Table 5]

[0175] Examples 1-18 The primer compositions were prepared by mixing all the components shown in Tables 6 and 7 in a glass container and shaking them at 100 rpm for 30 minutes on a low-profile laboratory orbital shaker (Ika KS 501 digital).

[0176] Using the priming procedure, the primers shown in Tables 6 and 7 were applied to the ABS and SS substrates. Subsequently, a 90° peel test at 300 mm / min (according to test method Finat No. 2) was performed using semi-structural adhesive tape 1 for Examples 1-14 and semi-structural adhesive tape 2 for Examples 15-18, after holding at room temperature for 24 hours. The results are shown in Tables 6 and 7 below. [Table 6] [Table 7]

[0177] Using the priming procedure, the primer compositions of Examples 4, 6, and 14 shown in Tables 6 and 7 were applied to various substrates shown in Table 8 below. Subsequently, a 90° peel test at 300 mm / min (according to test method Finat No. 2) was performed using semi-structural adhesive tape 1, after being held at room temperature for 24 hours. Static shear force tests and overlap shear tests were also performed on aluminum substrates. The results are shown in Table 8 below. [Table 8]

[0178] Adhesive System Examples 19-30 Using a priming procedure, the primer compositions of Examples 4, 6, and 14 shown in Tables 6 and 7 were applied to various substrates shown in Table 9 below. Subsequently, a 90° peel test at 300 mm / min (according to test method Finat No. 2) was performed using adhesive tapes obtained from 3M Company (St. Paul, MN) under the trade names "3M VHB TAPE LSE", "3M VHB TAPE GPH", "3M VHB TAPE 4941" (with an acrylate-based adhesive skin layer) and "3M ACRYLIC PLUS TAPE EX4011" (with a non-acrylate-based adhesive skin layer). The results are shown in Table 9 below. [Table 9]

[0179] The above description is provided to enable a person skilled in the art to implement the disclosures set forth in the claims and should not be construed as limiting the scope of the application as defined by the claims and their equivalents.

Claims

1. A primer composition comprising a polyacrylate dissolved or dispersed in water, wherein the polyacrylate is determined based on the total weight of monomer units in the polyacrylate. At least 20% by weight of methyl methacrylate units, A monomer unit comprising at least 15% by weight of at least one of a secondary amine, a tertiary amine, or a tertiary amide, At least 15% by weight of acrylic monomer units containing an alkyl group having at least 4 carbon atoms, 2.5% to 10% by weight of acrylic monomer units containing a carboxylic acid group. A primer composition containing the following:

2. The primer composition according to claim 1, wherein the monomer unit comprising at least one of the secondary amine, tertiary amine, or tertiary amide comprises at least one of 2-(N,N-dimethylaminoethyl)(meth)acrylate, 2-(N,N-diethylaminoethyl)(meth)acrylate, 2-(t-butylaminoethyl)(meth)acrylate, 2-(N,N-dimethylaminoethyl)(meth)acrylamide, 2-(N,N-diethylaminoethyl)(meth)acrylamide, 2-(t-butylaminoethyl)(meth)acrylamide, N-(meth)acryloylpiperidine, N-vinylcaprolactam, and N-vinyl-2-pyrrolidone.

3. The primer composition according to claim 1 or 2, wherein the methyl methacrylate units, monomer units comprising at least one of the secondary amine, tertiary amine, or tertiary amide, acrylic monomer units comprising an alkyl group having at least four carbon atoms, and acrylic monomer units comprising a carboxylic acid group together constitute at least 95% by weight of the monomer units in the polyacrylate.

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

5. The primer composition according to claim 4, wherein the solvent comprises at least one of propylene carbonate, alcohol, polyol, polyol ether, or dibasic acid ester.

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

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

8. A primer composition comprising a polymer dispersed in water and a solvent, wherein water accounts for at least 50% by weight of the primer composition, and the solvent comprises at least one of propylene carbonate, polyol, polyol ether, polyol ether ester, or dibasic acid ester.

9. The primer composition according to claim 8, wherein the primer composition comprises at least one of polyamide, polyurethane, or polyacrylate.

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

11. The primer composition according to claim 7 or 10, wherein the mole fraction of the dimer acid is 0.40 to 0.99, the mole fraction of the sulfonic acid-functional monomer is 0.01 to 0.20, and the mole fraction of at least one second diacid is 0 to 0.60, these based on the total number of moles of the combination of the dimer acid, the at least one second diacid, and the sulfonic acid-functional dicarboxylic acid or dicarboxylic acid ester, and the mole fraction of the oxyalkylenediamine is 0.005 to 0.10, and the mole fraction of at least one second diamine is 0.90 to 0.995, these based on the total number of moles of the combination of the oxyalkylenediamine, the further diamine, and the sulfonic acid-functional diamine.

12. An adhesive system comprising a primer composition according to 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 according to claim 12, wherein the adhesive tape is a semi-structural adhesive tape, the semi-structural adhesive tape includes an adhesive film, and the adhesive film is A first (meth)acrylate copolymer, Based on the weight of the first (meth)acrylate copolymer, at least 55% by weight of linear or branched alkyl (meth)acrylate monomer units; Based on the weight of the first (meth)acrylate copolymer, 15% to 40% by weight of (meth)acrylic acid monomer units, wherein if the first (meth)acrylate copolymer contains 15% by weight of (meth)acrylic acid monomer units, the first (meth)acrylate copolymer contains at least 5% by weight of high-Tg monomer monomer units based on the weight of the first (meth)acrylate copolymer, wherein the high-Tg monomer provides a homopolymer having a glass transition temperature of at least 50°C when homopolymerized with (meth)acrylic acid monomer units; Based on the weight of the first (meth)acrylate copolymer, 0.10% to 5% by weight of monomer units of a crosslinked monomer having two or more (meth)acrylate groups and Adhesive systems, including

14. The adhesive system according to claim 13, wherein the semi-structural adhesive tape is a multilayer 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 for manufacturing combined articles, Applying the primer composition according to any one of claims 1 to 11 to the surface of the first substrate, Applying a semi-structural tape to the primer composition on the surface of the first substrate, A method for manufacturing a combined article, including the following:

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

Images