Adhesive article release layer comprising a diphenyl carbamate compound

Abstract

Adhesive articles are described that include a substrate; a release layer disposed on the substrate, the release layer comprising a release compound; wherein the release compound has the following formula (Formula 1), wherein X is -CH2-; L is a divalent linking group comprising a urethane moiety; and R1 and R2 independently comprise a C4-C30 hydrocarbon group; and an adhesive bonded to the release layer. The release layer typically further comprises an organic polymer. Compositions comprising an organic polymer and a Formula 1 compound, as well as methods of making the compositions and release layers are also described.

Description

Summary of the Invention

[0001] In one embodiment, an adhesive article is described, the adhesive article comprising a substrate; an anti-adhesive layer disposed on the substrate, the anti-adhesive layer comprising an organic polymer and an anti-adhesive compound; wherein the anti-adhesive compound has the following formula:

[0002] in

[0003] X is -CH2-; L is a divalent linker containing a carbamate moiety; and R1 and R2 independently contain C4-C30 hydrocarbon groups; and An adhesive that bonds to the release layer.

[0004] In some embodiments, the anti-stick layer includes a first main surface near the substrate and a second main surface near the adhesive, wherein the second main surface contains a higher concentration of anti-stick compound than the first main surface.

[0005] In some embodiments, the organic polymer and the anti-sticking compound are soluble in an organic solvent selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, cyclopentanone, 2-butanone, xylene, 2-propanol, n-propanol, methanol, and mixtures thereof at a concentration of 10% by weight.

[0006] In some implementations, the organic polymer is thermoplastic.

[0007] In some implementations, the (e.g., thermoplastic) organic polymer is cross-linked.

[0008] In another embodiment, an anti-adhesive pad article is described, comprising a substrate; and an anti-adhesive layer disposed on the substrate, the anti-adhesive layer comprising an anti-adhesive compound of formula 1. The anti-adhesive layer typically also comprises an organic polymer.

[0009] In other embodiments, compositions comprising an organic polymer and a compound of formula 1 are described.

[0010] In other embodiments, methods for preparing the composition and the anti-stick layer are described. Attached Figure Description

[0011] Figure 1 This is a side view of an article, which includes a backing, an anti-stick coating on the main surface of the backing, and a pressure-sensitive adhesive on the opposite main surface of the backing. Figure 2 This is a side view of another article, which includes an anti-stick coated backing and a separate pressure-sensitive adhesive coated substrate; Figure 3This is a side view of another article, which includes a backing having an anti-stick coating on both main surfaces and a pressure-sensitive adhesive between the anti-stick coated surfaces.

[0012] Figure 4 The image shows the infrared spectrum of C18MDIC18.

[0013] Figure 5 The infrared spectrum of ODI-BPF-ODI. Detailed Implementation

[0014] Anti-stick compound

[0015] Compounds suitable for use as anti-sticking agents are typically prepared by reacting a diphenyl diisocyanate (e.g., MDI) with a hydroxyl-functionalized compound (i.e., a monofunctional alcohol) having a hydrocarbon chain of sufficient length. In a typical embodiment, the isocyanate is 4,4'-methylene diphenyl diisocyanate, as shown below:

[0016] In other embodiments, MDI may comprise other isomers, including 2,2'-methylene diphenyl diisocyanate, 3,3'-methylene diphenyl diisocyanate, and 2,4'-methylene diphenyl diisocyanate. MDI is commercially available from several suppliers, including Sigma Aldrich and Dow Inc.

[0017] Hydroxyl-functionalized compounds typically have saturated hydrocarbon chains, or in other words, contain alkyl groups. In other embodiments, the hydrocarbon chains may be unsaturated, or in other words, contain olefin or alkenyl groups.

[0018] Hydroxyl-functionalized compounds have the following formula: CH3(CH2)nOH The range of n is from 4 to 30 carbon atoms.

[0019] In some embodiments, the hydrocarbon group CH3(CH2)n- contains at least 6, 7, 8, 9, or 10 carbon atoms. In some embodiments, the hydrocarbon group CH3(CH2)n- contains at least 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms. In some embodiments, the hydrocarbon group CH3(CH2)n- contains no more than 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, or 18 carbon atoms. The hydrocarbon group may optionally be fluorinated.

[0020] Examples of straight-chain alcohols include, for example, octanol, decanol, lauryl alcohol, myristol, cetyl alcohol, cetearyl alcohol, stearyl alcohol, and betaine alcohol. Examples of straight-chain unsaturated higher alcohols include oleyl alcohol. Examples of branched higher alcohols include, for example, 2-hexyldecyl alcohol, 2-octyldodecyl alcohol, and 2-decyltetradecyl alcohol. An example of an alcohol having a combination of (e.g., aliphatic) hydrocarbon group and divalent aromatic hydrocarbon group (e.g., arylene group) is 4-n-butylphenol. Thus, the hydrocarbon group can be aliphatic, aromatic, or a combination of aliphatic and aromatic hydrocarbon groups.

[0021] In some embodiments, the hydrocarbon chain reactant (e.g., an alcohol or isocyanate) has a purity of at least 90%, 95%, or 97%. When a single reactant (e.g., an alcohol, octadecyl alcohol) is used and the reactant has a purity of at least 90%, 95%, or 97%, the percentage of hydrocarbon (e.g., alkyl) groups in the resulting anti-sticking compound having a specific chain length (e.g., 18) is the same as the purity of the reactant. In these embodiments, less than 10% by weight, 5% by weight, or 3% by weight of hydrocarbon (e.g., alkyl) groups have different chain lengths (due to the purity of the reactant).

[0022] In some embodiments, at least 90% of the total R1 and R2 hydrocarbon groups have a chain length of 8-30, 8-22, 8-18, 10-18, or 12-18. In some embodiments, at least 95%, 96%, or 97% of the total R1 and R2 hydrocarbon groups have a chain length of 8-30, 8-22, 8-18, 10-18, or 12-18.

[0023] In some embodiments, at least 90% of the total R1 and R2 groups have a hydrocarbon chain length of at least 10. In some embodiments, at least 95%, 96%, or 97% of the total R1 and R2 groups have a hydrocarbon chain length of at least 10.

[0024] In some embodiments, at least 90% of the total R1 and R2 groups have a hydrocarbon chain length of at least 12. In some embodiments, at least 95%, 96%, or 97% of the total R1 and R2 groups have a hydrocarbon chain length of at least 12.

[0025] In some embodiments, at least 90% of the total R1 and R2 groups have a hydrocarbon chain length of at least 18. In some embodiments, at least 95%, 96%, or 97% of the total R1 and R2 groups have a hydrocarbon chain length of at least 18.

[0026] In other embodiments, combinations of alcohols with different hydrocarbon chain lengths can be used to prepare diphenylmethane anti-sticking compounds.

[0027] The ratio of the molar number of alcohol to the molar number of diphenylmethane diisocyanate is usually 2:1 or slightly greater than 2:1, so that all isocyanate groups have reacted.

[0028] Anti-stick compounds have the following formula:

[0029] in

[0030] X is -CH2-; L is a divalent linker containing a carbamate moiety; and R1 and R2 independently contain C4-C30 hydrocarbon groups.

[0031] In typical embodiments, the urethane moiety represented by "L" is -NHC(O)O or -OC(O)NH-. However, in addition to the urethane moiety, L may also contain other organic linking groups, provided that the organic linking groups do not diminish the described anti-stick or contact angle properties. In some embodiments, R1 and R2 are both hydrocarbon groups, such as alkyl or alkenyl groups. In other embodiments, R1 and / or R2 contain a terminal aliphatic hydrocarbon group in combination with an aromatic group, such as in the case of using 4-n-butylphenol. Therefore, R1 and / or R2 may contain an aromatic moiety in combination with a terminal hydrocarbon group. It is also contemplated that the hydrocarbon group may contain substituents (e.g., fluoroalkyl groups).

[0032] The molecular weight of the anti-sticking compound is typically at least about 400 g / mol (398.5 g / mol when R1 and R2 are both butyl). In some embodiments, the molecular weight of the anti-sticking compound is at least 400 g / mol, 600 g / mol, or 700 g / mol (e.g., 791.3 g / mol when R1 and R2 are both C18). In some embodiments, the molecular weight of the anti-sticking compound is not greater than 1500 g / mol, 1400 g / mol, 1300 g / mol, 1200 g / mol, 1100 g / mol, 1000 g / mol, or 800 g / mol.

[0033] Anti-sticking compounds typically have a melt temperature Tm (the onset or maximum of endothermic reaction) of at least 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, or 130°C, as determined by differential scanning calorimetry. The melt temperature of the anti-sticking compound typically does not exceed 175°C, 170°C, 165°C, 160°C, 155°C, 150°C, 145°C, or 135°C. In some embodiments, the anti-sticking compound has a melt temperature Tm not exceeding 125°C, 120°C, 115°C, 110°C, 105°C, or 100°C.

[0034] When an anti-sticking compound is prepared by reacting diphenylmethane diisocyanate with a hydroxyl-functionalized compound as described above, the resulting compound has the following formula:

[0035] Alternatively, the anti-sticking compound can be prepared by reacting diphenylmethanediol with an isocyanate-functionalized compound having a long-chain hydrocarbon (e.g., octadecyl isocyanate). In this embodiment, the resulting compound has the following formula:

[0036] When the anti-sticking compound is derived from diphenylmethane diisocyanate or diphenylmethane diol, X is methylene (-CH2-).

[0037] The anti-stick layer typically comprises a combination of the anti-stick compound described herein and an organic polymer. The anti-stick layer may comprise a single (e.g., methylene) diphenylcarbamate compound or a mixture of compounds. Based on the total amount of the anti-stick compound and the organic polymer, the amount of the anti-stick compound is typically at least 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.05 wt%, 0.075 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%. A sufficiently low average peel force can typically be obtained with an anti-stick compound concentration of no more than 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, or 0.05 wt% based on the total amount of the anti-stick compound and the organic polymer.

[0038] However, the anti-stick layer and the mixture of (e.g., thermoplastic) organic polymer and anti-stick compound may contain a larger amount of anti-stick compound. Based on the total amount of anti-stick compound and organic polymer, the amount of anti-stick compound can be at least 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, or more. In some embodiments, based on the total amount of anti-stick compound and organic polymer, the amount of anti-stick compound may not exceed 90 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, 30 wt%, 20 wt%, or 10 wt%. Premixing the anti-stick compound with (e.g., thermoplastic) organic polymer can be particularly useful for providing very low concentrations of anti-stick compound. For example, a more concentrated mixture obtained by premixing the anti-stick compound with (e.g., thermoplastic) organic polymer can be fed into a hot extruder.

[0039] When an anti-adhesive layer is applied to a substrate, it is typically a homogeneous mixture of an anti-adhesive compound and an organic polymer. In some embodiments, such as when a large average peel value (e.g., greater than 200 g / in) is obtained, the anti-adhesive layer of the adhesive article may also comprise a homogeneous mixture of an anti-adhesive compound and an organic polymer. In other embodiments where a lower average peel value (e.g., less than 200, 100, or 50 g / in) is obtained, the anti-adhesive layer typically comprises a first primary surface adjacent to the substrate and a second primary surface adjacent to the adhesive. The second primary surface contains a higher concentration of the anti-adhesive compound than the first primary surface. Drying conditions may also promote the migration and self-assembly of the anti-adhesive compound at the second primary surface. Anti-adhesive compounds in which X is -CH2-, L is -NHC(O)O, and R1 and R2 are C18 contain 3.8% nitrogen based on atomic percentages. As demonstrated by X-ray photoelectron spectroscopy (XPS) analysis, for such anti-adhesive compounds, the amount of nitrogen at the surface of the anti-adhesive layer (in contact with the adhesive) can be at least 3 atomic% to 3.3 atomic%. Depending on the selection of X, L, R1, and R2, the atomic percentage of nitrogen can vary depending on the compound. However, the ratio of the atomic percentage of nitrogen at the surface of the release layer to the atomic percentage of nitrogen in the compound can represent a concentration ratio. For example, when both the release compound and the release layer surface have 3.8 atomic% nitrogen, 100% of the release compound is concentrated at the surface (3.8 / 3.8 = 1 × 100%). Similarly, when the compound has 3 atomic% nitrogen and the release layer surface has 1.5 atomic% nitrogen, 50% of the release compound is concentrated at the surface (1.5 / 3 = 0.5 × 100%). In some embodiments, at least 50%, 60%, 70%, 80%, 90%, or more of the release compound is concentrated at the surface of the release layer in contact with the adhesive.

[0040] The surface of the anti-stick layer can be characterized by its contact angle properties. In some embodiments, the static contact angle between the anti-stick layer (e.g., its second primary surface) and diiodomethane is at least 45 or 50 degrees, and up to 75, 80, or 85 degrees. In some embodiments, the static contact angle between the anti-stick layer (e.g., its second primary surface) and n-hexadecane is at least 30 or 35 degrees, and up to 45, 50, or 55 degrees. In some embodiments, the static contact angle between the anti-stick layer (e.g., its second primary surface) and dimethylsiloxane is at least 20 degrees, and up to 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 degrees. The contact angle indicates low surface energy and repulsion.

[0041] In typical implementations, the anti-stick compounds described herein are free of silicon (e.g., siloxanes, silyl groups) and / or fluorine. Therefore, the anti-stick layer may also be free of silicon and / or fluorine.

[0042] refer to Figure 5As shown in Figure 6, the urethane groups of the (e.g., anti-sticking) compounds contain readily available NH bonds, which have a high hydrogen bonding capacity. These urethane groups can act as both proton donors and acceptors. Through these strong intermolecular hydrogen bonds, the anti-sticking compounds form molecular assembly structures. The high absorbance of the urethane groups, determined by infrared spectroscopy, indicates hydrogen bonding. After one or two melt and cooling cycles, the peak absorbance of the urethane groups in the same wavelength range indicates the thermal stability of the (e.g., anti-sticking) compound.

[0043] It is presumed that organic polymers lacking hydrogen bonding or having low hydrogen bonding are preferably used to concentrate anti-stick compounds on a surface. Fewer hydrogen bonds between the organic polymer and the (e.g., anti-stick) compound promote the molecular assembly of the (e.g., anti-stick) compound. However, organic polymers with a larger number of hydrogen bonds are preferably used to uniformly distribute the anti-stick compound within the organic polymer. However, more hydrogen bonds between the organic polymer and the (e.g., anti-stick) compound can disrupt the molecular assembly of the (e.g., anti-stick) compound. The (e.g., anti-stick) compound may form hydrogen bonds with (meth)acrylate monomers more readily than (meth)acrylate polymers because (meth)acrylate polymers are less mobile than (meth)acrylate monomers. Furthermore, polyfunctional (meth)acrylate monomers having at least two or three (meth)acrylate monomers have multiple hydrogen donor and acceptor sites. Therefore, anti-stick layers are generally not (meth)acrylate polymers prepared by combining (e.g., anti-stick) compounds with (e.g., polyfunctional) (meth)acrylate monomers and curing the (meth)acrylate monomers. However, when using low concentrations of polyfunctional (meth)acrylate monomers as chemical crosslinking agents, the disruption of molecular assembly is minimal, especially when polyfunctional acrylates are combined with polymers. A lower re-adhesion value indicates reduced molecular assembly, which can lead to some transfer of (e.g., anti-stick) compounds or uncured (e.g., (meth)acrylate) monomers to the adhesive surface.

[0044] organic polymers

[0045] The release liner typically comprises one or more diphenylcarbamate compounds, as described herein, in combination with an organic polymer. The organic polymer improves the adhesion of the (e.g., methylene) diphenylcarbamate release liner compounds described herein to the substrate. The organic polymer also improves the durability of the release liner surface.

[0046] Preferred organic polymers may vary depending on the substrate and desired average peel characteristics. Suitable polymers include, for example, polyesters, acrylic polymers or in other words, poly(meth)acrylates, including polymethyl methacrylate and acrylic block copolymers, polyurethanes, styrene block copolymers, polyvinyl chloride (PVC), polycarbonate, polyetherimide, polyamide, polysulfone, polystyrene, polylactic acid (PLA), and polyolefins.

[0047] In some implementations, the organic (e.g., acrylic) polymer does not contain polymeric units of monomers with high concentrations of low glass transition temperature (Tg). Notably, when the organic polymer is polybutyl methacrylate and a silicone adhesive (such as the 3M 8403 tape used in the examples), a peel strength greater than 1000 g / in is achieved.

[0048] In some embodiments, the organic polymer is amorphous. Amorphous polymers are generally more soluble in organic solvents used for solvent-based anti-stick coatings compared to crystalline polymers. However, crystalline polymers are generally preferred for thermally extruded anti-stick layers. Alternatively, mixtures of amorphous and crystalline polymers can be used.

[0049] The molecular weight of the organic polymer is typically at least 10,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, or 500,000 g / mol (as measured by gel permeation chromatography using polystyrene standards). The molecular weight of the organic polymer is typically not greater than at least 2,000,000 g / mol, 1,500,000 g / mol, or 1,000,000 g / mol. In some embodiments, the organic polymer has a molecular weight not greater than 500,000 g / mol or 250,000 g / mol.

[0050] Mooney viscosity indicates molecular weight. In some embodiments, the Mooney viscosity of the organic (e.g., polyolefin) polymer is at least 40, 50, 60, or 70 mL (1+4) at 125°C. In some embodiments, the Mooney viscosity of the organic (e.g., polyolefin) polymer is not greater than 100, 90, or 80 mL (1+4) at 125°C. Mooney viscosity indicates molecular weight. In some embodiments, the Mooney viscosity is at least 10, 20, or 30 mL (1+4) at 100°C. In some embodiments, the Mooney viscosity is not greater than 50 or 40 mL (1+4) at 100°C.

[0051] In some embodiments, the organic polymer is a thermoplastic polymer (i.e., a polymer that softens and becomes more fluid at elevated temperatures and solidifies upon cooling). In some embodiments, the thermoplastic organic polymer has a thermal transition, i.e., a melt temperature or glass transition temperature, determined by differential scanning calorimetry, in the range of 100°C to 450°C. In some embodiments, the organic polymer has a thermal transition at temperatures below 400°C, 350°C, 300°C, or 250°C. While thermoplastic polymers can generally be reversibly melted and cured, it is also conceivable to crosslink the thermoplastic polymer after the release layer has been applied to the substrate. (e.g., thermoplastic) polymers can be crosslinked using chemical crosslinking agents or by exposure to photochemical (e.g., electron beam) radiation.

[0052] Melt flow index indicates that an organic polymer is thermoplastic and can be thermally processed by hot extrusion. Melt flow index (as measured using ASTM D1238-23A or ISO 01133) also indicates molecular weight. In some embodiments, the organic (e.g., polyolefin) polymer has a melt flow index of at least 2.5, 5, or 10 g / 10 min at temperatures ranging from 120°C to 200°C. In some embodiments, the melt flow rate temperature is 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, or 190°C. In some embodiments, the organic (e.g., polyolefin) polymer has a melt flow index of no more than 50, 25, 15, or 10 g / 10 min at temperatures ranging from 120°C to 200°C.

[0053] In other embodiments, the organic polymer can be melt-processed at higher temperatures. In this embodiment, the organic polymer has a melt flow index of at least 2.5, 5, or 10 g / 10 min at temperatures ranging from 200°C to 400°C. In some embodiments, the organic polymer has a melt flow index of at least 2.5, 5, or 10 g / 10 min at temperatures of 250°C, 300°C, 350°C, or 400°C.

[0054] In some implementations, the organic polymer of the anti-stick layer comprises polyolefins.

[0055] As used herein, polyolefin refers to a polymer comprising at least 50% by weight of a polyolefin portion. In some embodiments, the polyolefin polymer comprises at least 60%, 70%, 80%, 90% or more of a polyolefin portion.

[0056] The polyolefin moiety is typically derived from ethylene, propylene, and butene (including isobutene) and combinations thereof. In some embodiments, the polyolefin comprises (e.g., olefinic) unsaturated polyolefin moieties, such as butadiene. In some embodiments, the polyolefin comprises saturated or unsaturated polyolefin moieties having more than four carbon atoms, such as butadiene, hexene, and octene, particularly in the case of polyolefins prepared with metallocene catalysts. In some embodiments, the amount of unsaturated moieties (e.g., dienes) is at least 1, 2, 3, 4, or 5% by weight or mol% based on the total polymer. In some embodiments, the amount of unsaturated moieties (e.g., dienes) is not greater than 15 or 10% by weight or mol%. The polyolefin polymer can be a linear, branched, grafted, or block copolymer.

[0057] Polyolefins include, for example, high-density, medium-density, low-density and linear low-density polyethylene, ethylene / acrylic acid copolymers, ethylene / vinyl acetate copolymers, ethylene / propylene copolymers (including terpolymers), polypropylene, ethylene / propylene / diene copolymers (EPDM), and polymethylpentene.

[0058] In some embodiments, the organic polymer is a styrene block copolymer comprising styrene-terminated blocks and conjugated diene intermediate blocks, including, for example, styrene-isoprene-styrene (SIS), styrene-ethylene / butene-styrene block copolymers (SEBS), styrene-butadiene-styrene (SBS), styrene-isobutylene-styrene (SIBS), and acrylonitrile-butadiene-styrene block copolymers. When the organic polymer is a block copolymer comprising at least 50 wt% of a polyolefin portion, it can be characterized as a polyolefin. Based on the total weight of the block copolymer, the styrene block copolymer may contain at least 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of styrene-terminated blocks. Based on the total weight of the block copolymer, the amount of conjugated diene intermediate blocks is typically at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%. Each diene (such as butadiene or isoprene) typically has a degree of unsaturation. When partially hydrogenated, the amount of unsaturation can be even lower.

[0059] Various blends of polyolefin polymers can be used. Furthermore, one or more polyolefin polymers can be blended with other polymers containing less than 50% by weight of a polyolefin portion or without a polyolefin portion. In some embodiments, an organic (e.g., polyolefin) polymer (e.g., polystyrene) providing a higher average peel value can be combined with a second organic polymer (e.g., styrene block copolymer) providing a lower average peel value to adjust the peel value to a specific range. The weight ratio of the polyolefin (e.g., styrene block copolymer) to the second polymer (e.g., polystyrene) can be at least 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5, or 4:1. In this embodiment, the organic polymer blend / mixture comprises a polyolefin polymer (i.e., a styrene block copolymer), while the polymer mixture comprises less than 50% by weight of a polyolefin.

[0060] In some embodiments, the organic polymer is polyurethane. Polyurethane is prepared by reacting one or more polyols with one or more polyisocyanates. In some embodiments, the polyol has a number average molecular weight of at least 400, 450, or 500 Daltons (Da). In some embodiments, the polyol has a number average molecular weight of no more than 10,000 Da, 5,000 Da, or 2,000 Da. In some embodiments, the polyol may be at least one of polyester polyols, polyether polyols, polycarbonate polyols, and hydroxyl-terminated butadiene. Combinations of different types of polyols may be used.

[0061] Suitable polyester polyols include, but are not limited to, polybutylene adipate, polyethylene adipate, poly(diethylene adipate), polyhexane adipate, poly(neoprene adipate), poly(butylene adipate-co-phthalate), polycaprolactone, or copolymers thereof. Combinations of different polyester polyols may be used.

[0062] Common diisocyanates include, for example, dicyclohexylmethane-4,4'-diisocyanate, isoflavone diisocyanate, hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, m-xylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, poly(hexamethylene diisocyanate), 1,4-cyclohexylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4-diisocyanate, 1,4-butane diisocyanate, 1 8-Diisocyanate octane, 2,5-toluene diisocyanate, methylene bis(o-chlorophenyl diisocyanate), (4,4'-diisocyanate-3,3',5,5'-tetraethyl)diphenylmethane, 4,4'-diisocyanate-3,3'-dimethoxybiphenyl(o-anisidine diisocyanate), 5-chloro-2,4-toluene diisocyanate, 1-chloromethyl-2,4-diisocyanate benzene, tetramethyl-m-xylene diisocyanate, 1,12-diisocyanate dodecane, 2-methyl-1,5-diisocyanate pentane, 2,2,4-trimethylhexyl diisocyanate, or mixtures thereof.

[0063] Although polyols having at least three hydroxyl groups and / or polyisocyanates having at least three isocyanate groups can be used (e.g., in low concentrations), diols and diisocyanates are primarily used in the case of thermoplastic polyurethanes. Various thermoplastic polyurethanes are commercially available from Huntsman Corporation.

[0064] Polyurethanes can be characterized as crosslinked polyurethanes when they are prepared from polyols having at least three hydroxyl groups and / or polyisocyanates having at least three isocyanate groups at higher concentrations. Crosslinked organic polymers, including polyurethanes, are generally insoluble in organic solvents as described herein.

[0065] In other embodiments, the organic polymer is a thermosetting material that can be permanently cured into a solid state during (e.g., thermal) curing. In other embodiments, the organic polymer is a thermosetting resin that has already been (e.g., thermally) cured. Common thermosetting materials include melamine, polyester resins, urea-formaldehyde resins, vinyl ester resins, epoxy resins, polyimides, phenolic resins, and polymers prepared from cyclic dienes (e.g., polynorbornene). Such organic polymers typically have a glass transition temperature (Tg) of at least 50°C before curing. Thermosetting organic polymers and cured thermosetting resins typically have a Tg significantly higher than 50°C after curing. Before curing, the Tg of the organic polymer can be determined by dynamic mechanical analysis or differential scanning calorimetry. After curing, such materials are highly crosslinked, such that the resulting organic polymer typically does not exhibit a thermal transition (Tg or Tm) before the decomposition temperature of the organic polymer.

[0066] Organic polymers can contain a variety of functional groups that can participate in crosslinking. These functional groups can be located within the polymer backbone or as side groups. Other exemplary functional groups include, for example, alkynyl, halogen, thiol / mercapto, alkoxysilyl-, amine, nitrile, and acid / anhydride groups. Exemplary polymers with alkynyl functional groups include homopolymers and (e.g., block) copolymers of 4-(phenylethynyl)styrene, such as those described in LBSessions et al., Macromolecules, 2005, 38, 2116–2121. Exemplary polymers with halogen functional groups include halogenated (e.g., brominated) rubbers, such as brominated copolymers of butadiene and styrene available from Lanxess under the trade name LANXESS EMARALD INNOVATION 3000. Exemplary polymers having thiol / thiol functional groups include thiol-terminated polyether liquid polymers, such as those commercially available from Toray Industries, Inc. under the trade name POLYTHIOL QE-340M. Exemplary polymers having alkoxysilyl functional groups include silane-terminated polyethers, such as those commercially available from Wacker Industries, Inc. under the trade name WACKER GENIOSIL STP-E10. Exemplary polymers having amine functional groups include copolymers of poly(4-aminostyrene) and poly(l-lysine hydrobromide), which are commercially available from Polysciences under catalog number 02823. Exemplary polymers having nitrile functional groups include polyarylene ether nitrile, acrylonitrile butadiene rubber, and polycyanoarylene ether polymers described in US4812507. Acrylic polymers typically contain acidic functional groups (e.g., carboxylic acids or phosphonic acids). Various other polyolefins are commercially available that have anhydride (e.g., maleic anhydride) functional groups. Mixtures of polymers with functional groups can be used. Furthermore, organic polymers with functional groups can be combined with organic polymers lacking functional groups. In some embodiments, the type and amount of functional groups are selected to promote (e.g., anti-sticking) molecular assembly of the compound.

[0067] The release coating may comprise a single organic polymer or a mixture thereof. In some embodiments, the amount of the organic polymer (of the dried coating) is typically at least 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% by weight of the release coating.

[0068] Organic solvent solution

[0069] In some embodiments, the organic polymer is dissolved in an organic solvent to form an organic polymer solution. The organic polymer solution typically contains at least 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% of solid organic polymer. The solid weight percentage of the organic polymer in the organic polymer solution typically does not exceed 15 wt%.

[0070] Anti-sticking compounds are typically combined with organic polymer solutions. The anti-sticking compound is dispersible and preferably soluble in an organic solvent. In some embodiments, the organic solvent is selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, cyclopentanone, 2-butanone, and mixtures thereof. In some embodiments, the organic solvent also contains up to 30% of other solvents, such as isopropanol, n-propanol, ethanol, methanol, and ethyl acetate. Various solvent mixtures are described in the examples below. It should be understood that preferred solvents or solvent mixtures may differ for different organic polymers. In some embodiments, the anti-sticking compound may be dissolved in a first solvent or solvent mixture, and the organic polymer may be dissolved in a second solvent or solvent mixture. The first solvent or solvent mixture containing the anti-sticking compound is then combined with the second solvent or solvent mixture containing the organic polymer.

[0071] It should be understood that organic polymers soluble in organic solvents do not undergo crosslinking. However, as previously described, it is envisioned that organic polymers be crosslinked after application to a substrate. In other embodiments, organic polymers (e.g., polyurethanes) can be prepared by polymerizing their components (e.g., polyisocyanates and polyols) after application to a substrate. Crosslinked organic polymers are typically insoluble in organic solvents (e.g., the same organic solvents as those used in coating compositions) at a concentration of 5% or 10% solids (anti-stick composition) at 25°C. In some embodiments, crosslinked organic polymers are insoluble in organic solvents at concentrations ranging from 50% to 100% by weight. When the organic polymer is highly crosslinked, typically at least 60%, 70%, 80%, 90%, or more% are insoluble in organic solvents. When the organic polymer is less crosslinked, at least 10%, 20%, 30%, or 40% by weight may be insoluble in organic solvents.

[0072] additive

[0073] In some embodiments, the (e.g., release) composition optionally also includes one or more additives. Additives include, for example, one or more antioxidants, light (e.g., UV) stabilizers, homogenizers, heat stabilizers, rheology modifiers, colorants, UV or fluorescent dyes, antimicrobial compositions, fillers, plasticizers, etc. One or more additives may typically be present in the composition in an amount ranging from about 0.01% to 10% by weight based on the total composition, and may depend on the type of additive and the final properties of the release coating. In some embodiments, the total amount of additives is no more than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% by weight of the total solids composition (i.e., excluding any solvents that may be present).

[0074] (For example, anti-sticking) The composition optionally further comprises one or more chemical crosslinking agents. Chemical crosslinking agents typically contain at least two or three functional groups covalently bonded to the functional groups of an organic polymer. Exemplary functional groups include, for example, thiols / mercapto, amines, epoxy groups, hydroxyl groups, (e.g., alkyl)halides, and olefinically unsaturated functional groups, such as polyfunctional (meth)acrylates. Polyfunctional thiols / mercapto compounds (e.g., PETMP, CATMP, and DMPPG) can crosslink polymers having functional groups such as alkynes and nitriles. Polyfunctional amines (e.g., triethylamine) can crosslink polymers having functional groups such as halogens or nitriles. Polyfunctional epoxy compounds (e.g., glycerol polyglycidyl ether) can crosslink polymers having functional groups such as thiols / mercapto, amines, and acidic groups. Polyfunctional hydroxyl compounds (e.g., glycerol, ethylene glycol) can crosslink polymers having functional groups such as amines. Polyfunctional alkoxysilyl compounds can crosslink polymers having hydroxyl groups. Polyfunctional alkyl halides can crosslink polymers with functional groups such as amines. Organic acids (e.g., p-toluenesulfonic acid) can be used to crosslink polymers with nitrile groups.

[0075] Polyfunctional (meth)acrylate compounds can react with other free radicals, as well as thiols and amines. Examples of polyfunctional (meth)acrylate compounds include, but are not limited to, glyceryl dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-cyclohexanediol dimethacrylate, urethane dimethacrylate, and polyethylene glycol dimethacrylate. Examples of crosslinking monomers having three (meth)acryloyl groups include, but are not limited to, glyceryl trimethacrylate, trimethylolpropane trimethacrylate, 1,2,4-butanetriol trimethacrylate, and pentaerythritol trimethacrylate. Examples of crosslinking monomers having four or more (meth)acryloyl groups include, but are not limited to, pentaerythritol tetramethacrylate and sorbitol hexamethacrylate.

[0076] Various other chemical crosslinking agents and reactions are known. In some embodiments, as is known in the art, catalysts are included to accelerate crosslinking.

[0077] In some embodiments, (e.g., for anti-sticking purposes) the composition comprises a free radical initiator. The free radical initiator may be a thermal initiator or a photoinitiator.

[0078] Suitable thermal free radical initiators include various azo compounds, such as those commercially available under the trade name VAZO from Chemours Co. (Wilmington, DE, USA), including VAZO 67 (2,2'-azobis(2-methylbutyronitrile)), VAZO 64 (2,2'-azobis(isobutyronitrile)), VAZO 52 (2,2'-azobis(2,4-dimethylpentanitrile)), and VAZO 88 (1,1'-azobis(cyclohexanecarboxylonitrile)); various (e.g., organic) peroxides, such as benzoyl peroxide, cyclohexane peroxide, lauroyl peroxide, di-tert-amyl peroxide, tert-butyl peroxide, dicumyl peroxide; and those commercially available under the trade name LUPERSOL from Atofina Chemical, Inc. (Philadelphia, PA, USA). Commercially available peroxides (e.g., LUPERSOL 101, which is 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, and LUPERSOL 130, which is 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexyne); various hydroperoxides, such as tert-amyl hydroperoxide, tert-butyl hydroperoxide, and cumene hydroperoxide; and mixtures thereof.

[0079] Exemplary photoinitiators include benzoin ethers (e.g., benzoin methyl ether or benzoin isopropyl ether) or substituted benzoin ethers (e.g., anisole methyl ether). Other exemplary photoinitiators are substituted acetophenones, such as 2,2-diethoxyacetophenone or 2,2-dimethoxy-2-phenylacetophenone (available under the trade name IRGACURE 651 from BASF Corp., Florham Park, NJ, USA, or under the trade name ESACURE KB-1 from Sartomer, Exton, PA, USA). Other exemplary photoinitiators are substituted α-keto alcohols (such as 2-methyl-2-hydroxyacetophenone), aromatic sulfonyl chlorides (such as 2-naphthalenesulfonyl chloride), and photoactive oximes (such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime). Other suitable photoinitiators include, for example: 1-hydroxycyclohexylphenyl ketone (commercially available under the trade name IRGACURE 184), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available under the trade name IRGACURE 819), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (commercially available under the trade name IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone (commercially available under the trade name IRGACURE 369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one (commercially available under the trade name IRGACURE 907), and 2-hydroxy-2-methyl-1-phenylpropane-1-one (commercially available under the trade name DAROCUR). 1173 was purchased from Ciba Specialty Chemicals Corp. (Tarrytown, NY, USA).

[0080] Other free radical photoinitiators are acylphosphine oxides, such as those described in U.S. Patent 4,737,593 (Ellrich et al.).

[0081] Based on the total weight of the organic polymer component of the composition, the amount of chemical crosslinking agent (such as crosslinking monomers and / or free radical initiators) is typically in the range of 0.01 wt% to 5 wt%. Based on the total solids of the organic polymer and the anti-adhesive compound, this amount can be at least 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, or 1 wt%. The amount of chemical crosslinking agent is typically no more than 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, or 0.5 wt%.

[0082] Preparation method

[0083] A method for preparing a composition is described, comprising combining an organic polymer with at least one (e.g., methylene) diphenylcarbamate compound. When the composition also contains an organic solvent, the organic polymer and the anti-stick compound are preferably soluble in and / or dispersible in the organic solvent. Most preferably, a homogeneous solution is formed. To obtain a controlled and uniform anti-stick coating, a preferred coating method is capable of controlling the temperature of the coating solution at the point of application to the substrate. For example, when die-coating is performed in a roll-to-roll process, the solution supply container, supply lines, and coating die can be temperature-controlled.

[0084] In other embodiments, the precursor component of the organic polymer may be combined with at least one (e.g., methylene)diphenylcarbamate compound and an organic solvent. For example, in the case of polyurethane, the precursor component is a polyol and a polyisocyanate, as previously described. In this embodiment, the precursor component is polymerized in the presence of (e.g., methylene)diphenylcarbamate compound to form the organic polymer.

[0085] While it is preferred to combine the anti-stick compound with an organic polymer to promote the migration and self-assembly of the anti-stick compound at the main surface of the anti-stick layer that will contact the adhesive, it is also contemplated to coat an organic solvent solution containing only (e.g., methylene)diphenylcarbamate anti-stick compound (i.e., no organic polymer) onto the surface of an organic polymer substrate. In this embodiment, the surface layer may contain 100% (e.g., methylene)diphenylcarbamate anti-stick compound. However, if the solvent dissolves a portion of the organic polymer in the substrate, the surface layer may also contain a low concentration of organic polymer (e.g., less than 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, or 1 wt% organic polymer).

[0086] When the organic polymer is melt-processable, the organic polymer and the anti-stick compound can be bonded together by heating. Furthermore, the anti-stick layer can be applied to the substrate via hot extrusion. In this embodiment, the composition comprising the organic polymer and the anti-stick compound, as well as the method, are free of organic solvents. Melt-processable compositions and melt-processable substrates are also easier to recycle.

[0087] When preparing anti-stick pads, the method typically also includes applying the composition to a substrate. The anti-stick compositions described herein can be applied to a substrate (e.g., tape backing) using conventional coating techniques such as bar coating, gravure coating (e.g., direct, contact, reverse), three-roll and five-roll coating, air knife coating, spraying, notch bar coating, squeegee coating, slot coating (including application to tensioned webs), dip coating, curtain coating, and drag-knife coating.

[0088] Heated extrusion coating equipment can be used to maintain the anti-stick composition above its melting point. Organic solvent coating solutions are typically heated to temperatures ranging from 40°C to 80°C to maintain a homogeneous solution or to prevent organic polymer precipitation and compound release. This can include any combination of heated containers for delivery, such as heated tubing, heated pumping elements, heated coating dies / fluid application devices, and heated rollers (e.g., for conveying the substrate). Temperature can be controlled at the same or different temperatures throughout the coating process. Temperature can be controlled by any acceptable means, i.e., resistance heating bands, recirculated fluids (e.g., water, oil), infrared radiation, etc. In some embodiments, the anti-stick composition is maintained above the melting temperature of (e.g., methylene)diphenylcarbamate compounds when it is dispensed onto the substrate.

[0089] Depending on the coating method, the coating may be continuous or discontinuous. The thickness or mass per unit area of ​​the release coating may vary. In some embodiments, the coating has a thickness ranging from at least 0.0025 micrometers (25 nanometers) to a maximum of 25 micrometers. In some embodiments, the discontinuous coating has a mass per unit area ranging from at least 0.0025 grams per square meter (gsm) to a maximum of 25 gsm. In some embodiments, the thickness / mass per unit area is at least 0.05 micrometers or gsm, 0.1 micrometers or gsm, 0.2 micrometers or gsm, 0.3 micrometers or gsm, 0.4 micrometers or gsm, or 0.5 micrometers or gsm. In some embodiments, the thickness / mass per unit area is not greater than 10 micrometers or gsm, 9 micrometers or gsm, 8 micrometers or gsm, 7 micrometers or gsm, 6 micrometers or gsm, or 5 micrometers or gsm.

[0090] When an anti-stick layer is formed by applying a solution containing an organic solvent and an anti-stick compound, the organic solvent is removed by drying. The drying temperature and time may vary depending on the drying equipment used. In some embodiments, the coating containing the organic solvent is dried at room temperature or below the melt temperature of the anti-stick compound. In this embodiment, the dried coating may also be heat-treated at a temperature of at least 120°C, 130°C, 140°C, or 150°C. In some embodiments, the coating containing the organic solvent is dried at a temperature of at least 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C for a sufficient duration. In some embodiments, the drying and / or heat treatment temperature is equal to or higher than the melt temperature of the anti-stick compound. Such treatment conditions facilitate the concentration of the anti-stick compound on the surface of the anti-stick layer and promote the molecular assembly of the compound (e.g., anti-stick) on the surface opposite the substrate.

[0091] The non-stick layer prepared by hot extrusion can also be heat-treated at the above temperature.

[0092] In some embodiments, the method for preparing the release layer or film includes stretching and annealing. The substrate and release layer (e.g., co-extruded) can be stretched by at least 100%, 150%, 200%, 250%, 300%, or 350%. Stretching can include uniaxial or biaxial stretching. Stretching can reduce the thickness of the layer. When the organic polymer is fully crystallized, stretching leads to orientation, or in other words, an increase in birefringence. Annealing temperatures can be in the range of 170°C to 230°C.

[0093] When an organic polymer (or its precursor component) is crosslinked, the method may include exposing the applied organic polymer and (e.g., anti-sticking) compound to heat, photochemical radiation, or a combination thereof to cause the organic polymer to crosslink. In a typical embodiment, the aforementioned heat treatment temperature is suitable for crosslinking the organic polymer in the presence of a thermal free radical initiator.

[0094] One type of available photoluminescent light source is the light-emitting diode (“LED”). LED ultraviolet (UV) sources are advantageous because they provide ultraviolet light over a narrower wavelength range compared to other UV light sources, such as black light and mercury lamps. LED sources are commercially available and emit radiation, for example, at 395 nm or 405 nm.

[0095] Other photochemical light sources include UV black light and mercury lamps. Ultraviolet black light is a relatively low-intensity source, typically providing 10 mW / cm² in the wavelength range of 280 nm to 400 nm. 2 Or lower intensities (such as those measured according to procedures approved by the National Institute of Standards and Technology, for example, using a UVIMAP UM 365 LS radiometer manufactured by Electronic Instrumentation & Technology, Inc., Sterling, VA). Mercury lamps are higher-intensity, broadband ultraviolet sources, capable of providing typically greater than 10 mW / cm². 2 Preferably, it is between 15mW / cm 2 With 6000mW / cm 2 The strength between them. For example, 600mW / cm can be successfully used. 2 The intensity and approximately 1 second of exposure time. The intensity can be as low as 0.1 mW / cm². 2 Up to 6000mW / cm 2 And preferably at 0.5mW / cm 2 Up to 3000mW / cm 2 Within the range.

[0096] Release coatings can be applied to a variety of substrates, such as tape backing.

[0097] Suitable flexible substrates include, but are not limited to, paper, polymer-coated kraft paper, supercalendered or glassine kraft paper, and organic polymer films such as polyolefins, including poly(propylene), biaxially oriented polypropylene, poly(ethylene), poly(vinyl chloride) vinyl acetate; polycarbonate, poly(tetrafluoroethylene), polyester [e.g., poly(ethylene terephthalate)], poly(ethylene naphthalate), and polyimide films such as DuPont's KAPTON. ™ Polystyrene, cellulose acetate, ethyl cellulose, and polylactic acid (PLA).

[0098] Suitable substrates can also be formed from metals, metal foils, metallized (co)polymer films, or ceramic sheet materials. Substrates can also be in the form of fabric linings, such as synthetic fiber yarns or nonwoven webs or substrates, or combinations thereof.

[0099] In some embodiments, the thickness of the substrate is at least 0.5 mil, 1 mil, or 2 mil, and typically no more than 5 mil, 10 mil, or 15 mil.

[0100] One or both main surfaces of the substrate (e.g., backing) may also include an undercoat or be surface-treated (e.g., corona treatment) as known in the art to promote adhesion of an anti-stick coating, adhesive, or both.

[0101] Figure 1 An illustrative PSA article 100 is shown. The embodiment of the article (e.g., tape) includes an anti-stick coating 110 disposed on the main surface of a substrate (e.g., backing) 120 and a pressure-sensitive adhesive 130 disposed on the opposite main surface of 120.

[0102] Figure 2 Another PSA article 200 is depicted. This embodiment of the article includes an anti-stick coating 210 disposed on the main surface of a substrate (e.g., a backing) 220. A pressure-sensitive adhesive 230 is peelably bonded to the anti-stick coating 210. The pressure-sensitive adhesive is disposed on the main surface of a second substrate 221. Figure 3 Another PSA article 300 is depicted. This embodiment (e.g., tape) article includes anti-adhesive coatings 310 and 311 disposed on two main surfaces of a substrate (e.g., backing) 320, and a pressure-sensitive adhesive 330 peelably bonded to the anti-adhesive coating 311. One or both anti-adhesive coatings 310 and 311 are anti-adhesive coatings as described herein. When anti-adhesive coatings are disposed on two main surfaces, the anti-adhesive coatings may include the same or different anti-adhesive coatings, such as anti-adhesive coatings with different amounts of anti-adhesive compound.

[0103] When an organic polymer and (e.g., an anti-stick) compound are thermally extruded to a sufficient thickness, a self-supporting anti-stick liner film is formed without a substrate. The organic polymer substrate layer may be co-extruded with one or more anti-stick layers.

[0104] Adhesive articles can be tapes, strips, sheets (e.g., perforated sheets), labels, rolls, webs, reels, and kits (e.g., an object to be mounted and adhesive tape for mounting the object).

[0105] adhesives

[0106] The non-stick coatings described herein are suitable for use with a variety of adhesive compositions. Suitable (e.g., pressure-sensitive) adhesives include natural or synthetic rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, vinyl alkyl ether pressure-sensitive adhesives, silicone pressure-sensitive adhesives, polyester pressure-sensitive adhesives, polyamide pressure-sensitive adhesives, poly-α-olefin, polyurethane pressure-sensitive adhesives, and styrene block copolymer-based pressure-sensitive adhesives.

[0107] The adhesive can be an organic solvent-based, water-based emulsion, a hot melt (e.g., as described in US 6,294,249), a thermally activated, or photochemically irradiated (e.g., electron beam, ultraviolet light) curable adhesive. In some embodiments, the organic solvent is removed from the pressure-sensitive adhesive before contacting the adhesive with the release coating described herein. In other embodiments, the hot melt adhesive is contacted with the release coating at a temperature below the melt temperature of the release coating composition. In some embodiments, dry lamination of the adhesive can provide a lower peel value than solvent-coated adhesives.

[0108] In a typical implementation, the adhesive is a pressure-sensitive adhesive, which typically has a strength of less than 3 × 10⁻⁶ ppm as measured by dynamic mechanical analysis at room temperature (25°C) at a frequency of 1 Hz. 6 Storage modulus (E') in dynes / cm.

[0109] Pressure-sensitive adhesives may also contain one or more suitable additives, such as crosslinking agents (e.g., polyfunctional (meth)acrylate crosslinking agents (e.g., TMPTA), epoxy crosslinking agents, isocyanate crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, etc.), tackifiers (e.g., phenol-modified terpenes and rosin esters, such as glycerol esters of rosin and pentaerythritol esters of rosin, as well as C5 and C9 hydrocarbon tackifiers), thickeners, plasticizers, fillers, antioxidants, UV absorbers, antistatic agents, surfactants, leveling agents, colorants, flame retardants, and silane coupling agents.

[0110] It should be understood that different pressure-sensitive adhesive compositions are preferred for different anti-stick compositions. It should also be understood that different types of adhesive products have different preferred peel properties.

[0111] The release layer can be evaluated using various commercially available tape adhesive compositions, including those described in the following examples. The release layer can also be evaluated using test tape 1, which has a 25-micron-thick hot-melt adhesive layer disposed on a 50-micron-thick corona-treated BOPP film. This hot-melt adhesive layer comprises a mixture of 100 parts SIS block copolymer (with a styrene content of 14.3%, a coupling efficiency of 88%, and a melt index of 9 g / 10 min (condition G)), 85 parts tackifying resin (C9 modified C5 with a softening point of 87°C), and 2 parts antioxidant.

[0112] In some embodiments, the adhesive is a silicone adhesive. Silicone adhesives can advantageously form strong bonds with many materials, including silicone release liner. Therefore, developing release liner for silicone adhesives is particularly challenging.

[0113] Silicone adhesives typically contain silicone materials according to the following formula, which shows a siloxane backbone having aliphatic and / or aromatic substituents:

[0114] R1, R2, R3, and R4 are independently selected from alkyl and aryl groups, each R5 is an alkyl group, and n and m are integers, with at least one of m or n being non-zero. In some embodiments, one or more of the alkyl or aryl groups may contain a halogen substituent, such as fluorine. For example, in some embodiments, one or more of the alkyl groups may be –CH2CH2C4F9.

[0115] In some embodiments, R5 is a methyl group, i.e., the nonfunctionalized polydiorganosiloxane material is end-capped with a trimethylsiloxy group. In some embodiments, R1 and R2 are alkyl groups, and n is zero, i.e., the material is poly(dialkylsiloxane). In some embodiments, the alkyl group is a methyl group, i.e., poly(dimethylsiloxane) (“PDMS”). In some embodiments, R1 is an alkyl group, R2 is an aryl group, and n is zero, i.e., the material is poly(alkylarylsiloxane). In some embodiments, R1 is a methyl group, and R2 is a phenyl group, i.e., the material is poly(methylphenylsiloxane). In some embodiments, R1 and R2 are alkyl groups, and R3 and R4 are aryl groups, i.e., the material is poly(dialkyldiarylsiloxane). In some embodiments, R1 and R2 are methyl groups, and R3 and R4 are phenyl groups, i.e., the material is poly(dimethyldiphenylsiloxane).

[0116] In some embodiments, the nonfunctionalized polydiorganosiloxane material may be branched. For example, one or more of the R1, R2, R3 and / or R4 groups may be straight-chain or branched siloxanes having alkyl or aryl (including halogenated alkyl or aryl) substituents and an R5 terminal group.

[0117] As used herein, "nonfunctional group" refers to an alkyl or aryl group consisting of carbon, hydrogen, and, in some embodiments, halogen (e.g., fluorine) atoms. As used herein, "nonfunctionalized polydiorganosiloxane material" refers to a material in which R1, R2, R3, R4, and R5 groups are nonfunctionalized groups.

[0118] Generally speaking, functionalized organosilicon systems include specific reactive groups (e.g., hydrogen, hydroxyl, vinyl, allyl, or acrylic groups) attached to the polysiloxane backbone of the starting material. As used herein, "functionalized polydiorganosiloxane material" refers to at least one of the R groups in Formula 2 being a functional group.

[0119] In some embodiments, the functionalized polydiorganosiloxane material comprises at least two R groups as functional groups. Generally, the R groups of Formula 2 can be chosen independently. In some embodiments, at least one functional group is such as a hydride group, hydroxyl group, alkoxy group, vinyl group, epoxy group, and acrylate group. When the polydiorganosiloxane is a nonfunctional polydiorganosiloxane, the polydiorganosiloxane does not contain such functional groups.

[0120] In addition to the functional R groups, some of the R groups may also be non-functional groups, such as alkyl or aryl groups, including haloalkyl (e.g., fluoro) groups and aryl groups. In some embodiments, the functionalized polydiorganosiloxane material may be branched. For example, one or more of the R groups may be straight-chain or branched siloxanes with functional and / or non-functional substituents.

[0121] In addition to other parts in the main chain, other organosilicon materials also contain siloxane moieties, such as urea, amide, oxalamide, and carbamate.

[0122] Suitable siloxane polyurea block copolymers can have the following formula 3:

[0123] in

[0124] Each R is a portion, which is independently: an alkyl portion having about 1 to 12 carbon atoms and being substituted, for example, a trifluoroalkyl or vinyl group, a vinyl radical, or a more advanced alkenyl radical; a cycloalkyl portion having about 6 to 12 carbon atoms and being substituted, for example, an alkyl, fluoroalkyl, or vinyl group; or an aryl portion having about 6 to 20 carbon atoms and being substituted, for example, an alkyl, cycloalkyl, fluoroalkyl, or vinyl group; or R is a perfluoroalkyl group as described in U.S. Patent No. 5,028,679, or a fluorinated group as described in U.S. Patent No. 5,236,997, or a group containing a perfluoroether as described in U.S. Patent Nos. 4,900,474 and 5,118,775; typically at least 50% of the R portion is a methyl radical, and the remainder is a monovalent alkyl or substituted alkyl radical, alkenyl radical, phenyl radical, or substituted phenyl radical having 1 to 12 carbon atoms; Each Z is a polyvalent group, which is an arylene or arylene alkyl group having about 6 to 20 carbon atoms, an alkylene or cycloalkylene group having about 6 to 20 carbon atoms, and in some embodiments, Z is 2,6-tolyl, 4,4'-methylenediphenylene, 3,3'-dimethoxy-4,4'-biphenylene, tetramethyl-m-xylylene, 4,4'-methylenedicyclohexylene, 3,5,5-trimethyl-3-methylenecyclohexylene, 1,6-hexamethylene, 1,4-cyclohexylene, 2,2,4-trimethylhexylene, and mixtures thereof; Each Y is a polyvalent group, which is independently an alkylene group with 1 to 10 carbon atoms, an arylene group with 6 to 20 carbon atoms, or an aryl group; Each D is selected from hydrogen, alkyl groups with 1 to 10 carbon atoms, phenyl groups, and groups that complete a ring structure containing B or Y to form a heterocycle; Wherein B is a polyvalent group selected from the following: alkylene, arylene, cycloalkylene, phenylene, heteroalkylene, including, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene and copolymers and mixtures thereof; m is a number from 0 to approximately 1000; n is a number that is at least 1; and p is at least 10, in some implementations it is 15 to about 2000, or even a number from 30 to 1500.

[0125] Available siloxane polyurea block copolymers are disclosed in, for example, the following patents: U.S. Patents Nos. 5,512,650, 5,214,119, 5,461,134 and 7,153,924, and PCT Publications Nos. WO 96 / 35458, WO 98 / 17726, WO 96 / 34028, WO 96 / 34030 and WO 97 / 40103.

[0126] Another class of useful elastomeric siloxane polymers that can be prepared from amine-functionalized polysiloxanes are oxalamide polymers, such as polydiorganosiloxane-polyethylene glycol block copolymers. Examples of polydiorganosiloxane-polyethylene glycol block copolymers are shown, for instance, in U.S. Patent Publication No. 2007 / 0148475. Polydiorganosiloxane-polyethylene glycol block copolymers contain at least two repeating units of Formula 4:

[0127] In this formula, each R 1 Independently alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with alkyl, alkoxy, or halogen, wherein at least 50% of R 1 The group is methyl. Each Y is independently an alkylene, arylene, or combination thereof. The subscript n is independently an integer from 40 to 1500, and the subscript p is an integer from 1 to 10. Group G is a divalent group, which is a residue unit equal to formula R. 3 HN-G-NHR 3 Diamine minus two –NHR 3 Group. Group R 3 It is hydrogen or an alkyl group (e.g., an alkyl group having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R 3 Together with G and the nitrogen that they are attached to, they form heterocyclic groups (e.g., R). 3 HN-G-NHR 3 For piperazine, etc.). Each asterisk ( ) indicates the connection site between the repeating unit and another group in the copolymer (such as, for example, another repeating unit of formula 4).

[0128] Applicable to R in Equation 3 1 The alkyl group typically has 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, and isobutyl. Applicable to R 1 The haloalkyl group often consists of only a portion of the hydrogen atoms of the corresponding alkyl group that has been substituted with a halogen. Exemplary haloalkyl groups include chloroalkyl groups and fluoroalkyl groups having 1 to 3 halogen atoms and 3 to 10 carbon atoms. For R 1Suitable alkenyl groups typically have 2 to 10 carbon atoms, optionally substituted with halogens (e.g., fluorine). Exemplary alkenyl groups often have 2 to 8, 2 to 6, or 2 to 4 carbon atoms, such as vinyl, n-propenyl, and n-butenyl. Applicable to R 1 The aryl group typically has 6 to 12 carbon atoms. A phenyl group is an exemplary aryl group. The aryl group may be unsubstituted or substituted with an alkyl group (e.g., an alkyl group having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), an alkoxy group (e.g., an alkoxy group having 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms), or a halogen group (e.g., chlorine, bromine, or fluorine). Applicable to R 1 Aryl groups typically contain an alkylene group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms. In some exemplary aryl groups, the aryl group is phenyl, and the alkylene group has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms (i.e., the structure of the aryl group is alkylene-phenyl, wherein the alkylene group is bonded to the phenyl group).

[0129] At least 50% of R 1 The group is methyl. For example, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, or at least 99% of R. 1 The group can be methyl. The remaining R... 1 The group may be selected from alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl groups having at least two carbon atoms, or aryl groups substituted with alkyl, alkoxy, or halogen.

[0130] Each Y in Formula 3 is independently an alkylene, arylene, or combination thereof. Suitable alkylene groups typically have up to 10, 8, 6, or 4 carbon atoms. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. Suitable arylene groups typically contain an arylene group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. In some exemplary arylene groups, the aryl portion is a phenylene group. That is, the divalent arylene group is a phenylene-alkylene group, wherein the phenylene group is bonded to an alkylene group having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used herein with respect to group Y, "combination thereof" refers to a combination of two or more groups selected from alkylene and arylene groups. The combination can be, for example, a single aryl alkyl group bonded to a single alkyl group (e.g., alkyl-aryl-alkyl group). In an exemplary alkyl-aryl-alkyl group, the aryl group is a benzene group, and each alkyl group has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0131] Each subscript n in Equation 3 is an independent integer from 40 to 1500. For example, the subscript n can be an integer of up to 1000, up to 500, up to 400, up to 300, up to 200, up to 100, up to 80, or up to 60. The value of n is often at least 40, at least 45, at least 50, or at least 55. For example, the subscript n can be in the range of 40 to 1000, 40 to 500, 50 to 500, 50 to 400, 50 to 300, 50 to 200, 50 to 100, 50 to 80, or 50 to 60.

[0132] The subscript p is an integer from 1 to 10. For example, the value of p is often an integer of at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, or at most 2. The value of p can be in the range of 1 to 8, 1 to 6, or 1 to 4.

[0133] In Formula 3, group G is a residue unit, which is equal to formula R. 3 HN-G-NHR 3 The diamine compound minus two amino groups (i.e., -NHR) 3 Group R). 3 It is hydrogen or an alkyl group (e.g., an alkyl group having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R 3 It forms heterocyclic groups with G and the nitrogen that it shares with (e.g., R). 3 HN-G-NHR 3 (For piperazine). The diamine may have primary or secondary amino groups. In most embodiments, R 3 It is hydrogen or alkyl. In many embodiments, both amino groups of the diamine are primary amino groups (i.e., R...). 3 All groups are hydrogen, and the diamine has the formula H2N-G-NH2.

[0134] In some embodiments, G is an alkylene, heteroalkylene, polydiorganosiloxane, aryl, arylalkylene, or a combination thereof. Suitable alkylenes typically have 2 to 10, 2 to 6, or 2 to 4 carbon atoms. Exemplary alkylene groups include ethylene, propylene, butylene, etc. Suitable heteroalkylenes are often polyoxyalkylenes, such as polyoxyethylene having at least 2 ethylene units, polyoxypropylene having at least 2 propylene units, or copolymers thereof. Suitable polydiorganosiloxanes include polydiorganosiloxane diamines of Formula 1 above, minus two amino groups. Exemplary polydiorganosiloxanes include, but are not limited to, polydimethylsiloxanes having an alkylene Y group. Suitable arylalkylene groups typically contain an aryl group having 6 to 12 carbon atoms bonded to an alkylene group having 1 to 10 carbon atoms. Some exemplary arylalkyl groups are benzene-alkyl groups, wherein the benzene group is bonded to an alkyl group having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. As used herein with respect to group G, “combinations of them” refers to a combination of two or more groups selected from alkylene, heteroalkylene, polydiorganosiloxane, aryl, and arylalkylene groups. Combinations can be, for example, arylalkyl groups bonded to an alkyl group (e.g., alkylene-aryl-alkyl group). In an exemplary alkylene-aryl-alkyl group, the aryl group is a benzene group, and each alkyl group has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.

[0135] Polydiorganosiloxane-polyethylene glycol amide often does not contain the formula -R a The group -(CO)-NH-, where R a It is alkylene. All carbonyl imino groups along the main chain of the copolymer material are part of an oxaloyl group (i.e., a -(CO)-(CO)-NH- group). That is, any carbonyl group along the main chain of the copolymer material is bonded to another carbonyl group and is part of an oxaloyl group. More specifically, polydiorganosiloxane-polyethylene amide has multiple aminooxaloyl amino groups.

[0136] Another class of available elastomeric siloxane polymers are amide-based polysiloxane polymers. Similar to urea-based polymers, these polymers contain amide bonds (-N(D)-C(O)-) instead of urea bonds (-N(D)-C(O)-N(D)-), where C(O) represents a carbonyl group and D is a hydrogen or alkyl group.

[0137] Another class of available elastomeric siloxane polymers are urethane-based siloxane polymers, such as siloxane polyurea-urethane block copolymers. These siloxane polyurea-urethane block copolymers comprise the reaction product of polydiorganosiloxane diamine (also known as siloxane diamine), diisocyanate, and organic polyol. Structurally, these materials are very similar to those of Formula I, except that the -N(D)-BN(D)- bonds are replaced by -OBO- bonds. Examples of such polymers are described, for example, in U.S. Patent No. 5,214,119.

[0138] Organosilicon materials comprising a siloxane backbone, optionally combined with other components, can be oils, fluids, adhesives, elastomers, or resins, such as brittle solid resins. Materials with lower molecular weights and lower viscosity are referred to as fluids or oils, while materials with higher molecular weights and higher viscosity are referred to as adhesives; however, there is no clear distinction between these terms. Silicone oils are commercially available (e.g., from Wacker), with viscosities ranging from 0.65 to 1,000,000 mPa at 25°C. In typical embodiments, higher viscosity (e.g., nonfunctional) liquid polydiorganosiloxanes are preferred. In some embodiments, the liquid polydiorganosiloxane has a viscosity at 25°C of at least 50,000, 100,000, 250,000, 500,000, 750,000, or 1,000,000 mPa. When using polydiorganosiloxane adhesives, the viscosity at 25°C can exceed 1,000,000 mPa. sec.

[0139] In some embodiments, the silicone adhesive also comprises a tackifying silicate resin. Suitable tackifying silicate resins include those composed of the following structural units: M (i.e., monovalent R'3SiO). 1 / 2 unit), D (i.e., divalent R'2SiO), 2 / 2 Unit), T (i.e., trivalent R'SiO), 3 / 2 unit) and Q (i.e., tetravalent SiO) 4 / 2 (units) and combinations thereof. Typical exemplary silicate resins include MQ silicate tackifying resin, MQD silicate tackifying resin, and MQT silicate tackifying resin. These silicate tackifying resins typically have a number-average molecular weight in the range of 100 g / mol to 50,000 g / mol, for example, 500 g / mol to 15,000 g / mol, and the R' group is typically methyl.

[0140] MQ tackifying silicate resins are copolymer resins in which each M unit is bonded to a Q unit, and each Q unit is bonded to at least one other Q unit. Some Q units are bonded only to other Q units. However, some Q units are bonded to hydroxyl groups to obtain HOSiO. 3 / 2 Unit (i.e., "T") OH The unit indicates the content of some silicon-bonded hydroxyl groups in the tackifying silicate resin.

[0141] The content of silicon-bonded hydroxyl groups (i.e., silanols) on the MQ resin can be reduced to no more than 1.5 wt%, 1.2 wt%, 1.0 wt%, or 0.8 wt% based on the weight of the silicate tackifying resin. This can be achieved, for example, by reacting hexamethyldisilazane with the silicate tackifying resin. Such a reaction can be catalyzed, for example, with trifluoroacetic acid. Alternatively, trimethylchlorosilane or trimethylsilylacetamide can be reacted with the silicate tackifying resin, in which case no catalyst is required.

[0142] The MQD tackifying silicone resin is a terpolymer having M, Q, and D units. In some embodiments, some methyl R' groups in the D unit can be replaced with vinyl (CH2=CH-) groups (“D…”). Vi (M, Q, and T units). MQT silicate tackifying resin is a terpolymer containing M, Q, and T units.

[0143] Suitable silicate tackifying resins are commercially available from sources such as Dow Corning (e.g., DC 2-7066), Momentive Performance Materials (e.g., SR545 and SR1000), and Wacker Chemie AG (e.g., BELSIL TMS-803).

[0144] In some embodiments, the polydiorganosiloxane composition layer comprises (e.g., silicate) tackifying resin in an amount of at least 5%, 10%, 15%, 20%, 25%, 30%, or more of the total silicone adhesive composition.

[0145] The average peel strength and re-adhesion of the anti-adhesive layer can be evaluated according to the test methods described in the examples.

[0146] In some embodiments, at a peel rate of 60 inches (152 cm) / minute, the average initial peel force of the release layer is typically in the range of 5 g / inch (2.54 cm) to 800 g / inch (11.16 g / cm to 167.4 g / cm). The average initial peel force is typically reported after aging at 50°C for 1, 2, 5, 7, 8, or 19 days. In some embodiments, the average initial peel force of the release coating is at least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 g / inch. In some embodiments, a higher average initial peel force may be preferred to prevent self-unwinding of the tape roll or to provide greater holding force in the event of over-adhesion, such as for packaging tapes and medical tapes.

[0147] In some embodiments, such as industrial silicone adhesive articles, the release layer provides an average initial peel force of at least 500, 600, 700, or 800 g / in. In other embodiments, the average peel force is no greater than 500, 400, 300, 200, 100, or 50 g / in.

[0148] After aging at 50°C for 1, 3, or 13 days, re-adhesion is typically in the range of 25 to 500 g / in. In some embodiments, the re-adhesion is at least 50 or 100 g / in. In some embodiments, the re-adhesion is no greater than 400, 300, 200, or 100 g / in. A low re-adhesion value may indicate that the release agent or release compound has transferred to the adhesive surface.

[0149] The present invention is illustrated by the following examples.

[0150]

[0151] Contact angle measurement

[0152] Contact angle measurements were performed on the dried coated samples. Measurements were performed using ready-to-use reagent-grade hexadecane (Aldrich), diiodomethane (Aldrich), DMS-14, and deionized water filtered through a filtration system from Millipore Corporation (Billerica, MA), USA, on a video contact angle analyzer (product number VCA-2500XE), available from AST Products (Billerica, MA), USA. Recorded values ​​are the average of measurements obtained by measuring at least three drops on their respective left and right sides, and are shown in the table. The droplet volume for static measurements was 5 mL.

[0153] Peel test

[0154] Peel tests were performed using an iMass TL-2300 peel tester. Averaged data were collected using DataLink software. The method used had the following instrument settings: initial delay: 2 seconds, averaging time: 5 seconds, test time (plate stop mode), force unit: grams, speed unit: inches / minute, test speed: 60 inches / minute – 152.4 cm / minute. The release liner (coated substrate or film) to be tested was adhered to the instrument slider, close to the force gauge, with both ends kept flat with tape to avoid friction with the force probe test clamp. The force probe was aligned with each piece of tape and secured with the force test clamp. Before testing, the slider was manually removed from the probe to remove any looseness. The release liner was cooled to room temperature and manually laminated to the adhesive surface of the tape (e.g., 3M 8403 or Scotch Magic tape) and placed in a forced-ventilation oven at 50°C for the specified number of days. After aging, the samples were conditioned at room temperature for at least 1 hour. Peel force measurements were performed at room temperature.

[0155] Re-adhesion test

[0156] For the re-adhesion test, the tape was adhered to a glass substrate, pre-cleaned with isopropyl alcohol, and its peel strength was compared with that of the control 3M 8403 tape. Conditions were similar to the peel test method, except that the peel speed was set at 12 inches / minute and the average data collection time was 20 seconds. When using SPU or rSPOx PSA, the adhesive on the backing was removed from the release liner, laminated onto a 1" wide primed PET sheet, removed from its backing, and laminated onto clean glass. Re-adhesion strength was measured by peeling the PET with adhesive from the glass at 12 inches / minute. Some peel tests were also performed at 1200 inches / minute to determine the rate dependence of peel strength using the formulations described in the examples.

[0157] Melting point determination

[0158] The melting point of the anti-sticking additive was measured using a dynamic scanning calorimeter (DSC instrument) TA Instruments Q2000, using a temperature ramp from room temperature to 200°C at 10°C / min, cooling to 0°C at 5°C / min, and then a second heating to 200°C (or higher) at 10°C / min.

[0159] Preparation of anti-sticking compounds with urethane linking groups

[0160] MDI-n-Butyl(C4MDIC4)

[0161] To a 100 ml single-necked round-bottom flask, place a stir bar, methylene diphenyl diisocyanate (25.0 g, mw = 250.25), and n-butanol (14.9 g, mw = 74.12). Mix them in their pure form and heat to 100-110 °C. The diisocyanate melts into a liquid and reacts rapidly with the alcohol to give a white solid. Heat the reaction mixture until the solid melts into a liquid and until no liquid reflux is observed, to ensure that all alcohol has been consumed. ATR-IR measurements of the solid indicate complete consumption of the isocyanate groups. Melting point determined by DSC: initial temperature 98.7 °C on the first heating, and peak temperature 109.7 °C.

[0162] C6MDIC6

[0163] 23.35 g of MDI was added to a dry 250 mL Schlenk flask under argon atmosphere. While stirring the mixture with a PTFE-coated magnetic stir bar, 23.5 mL of 1-hexanol was added dropwise over 3 minutes. Exothermic reaction was observed, with the temperature rising to 96.7 °C within 15 minutes. The mixture solidified and was further heated above its melting point to 140 °C over 30 minutes using a heating mantle. Upon cooling, crystal formation was observed at 109 °C. ATR-IR analysis of the sample showed no residual isocyanate group bands. 41.97 g was recovered without further purification. The melting point, determined by DSC, was 95 °C on initial heating and peaked at 108.9 °C.

[0164] C8MDIC8

[0165] Add 25.02 g of solid MDI (mw = 250.25) and 26.05 g of 1-octanol (mw = 130.2) to a round-bottom flask. Assemble the flask with a water condenser equipped with a nitrogen inlet. Heat the mixture to approximately 80-100°C until the solution becomes a clear liquid. Reheat the solution for 1 hour until all the alcohol is consumed. Cool the solution to room temperature, and the product solidifies. Its IR spectrum shows the complete disappearance of the isocyanate group band. Melting point determined by DSC: the endothermic peak begins at 111°C and peaks at 121°C upon first heating.

[0166] C10MDIC10

[0167] To a 100 mL single-necked round-bottom flask, place a stir bar, methylene diphenyl diisocyanate (12.51 g, mw = 250.25), and 1-decyl alcohol (15.83 g, mw = 158.28). Mix them in pure form and heat to 100 °C–110 °C. The diisocyanate melts into a liquid and reacts rapidly with the alcohol to give a white solid. Add 25 mL of toluene solvent to the reaction mixture and heat until all the solid dissolves in the toluene. Cool the mixture to recrystallize, thus completing the reaction. Remove the toluene to obtain a 100% yield. Melting point determined by DSC: the endothermic peak begins at 120.1 °C and peaks at 124.4 °C upon first heating.

[0168] C12MDIC12

[0169] Under argon atmosphere, 36.747 g of 1-dodecaneol, 24.67 g of MDI, and a magnetic stir bar were added to a dry 250 mL Schlenk flask. Heating was initiated using an autotransformer at 50% / 120 V with the heating mantle heated to above 80 °C. Rapid exothermic reaction was observed to 124 °C, and the product began to solidify. Further heating to 136 °C was used to remelt the mixture to allow continued stirring, followed by further heating to 150 °C over 25 minutes, and then slow cooling to room temperature. After one hour of cooling, the solid was sampled and analyzed by ATR-IR, which showed the disappearance of the isocyanate band. The solid was crushed and collected without further purification, yielding 60.54 g (98.6%) after transfer. Melting point determined by DSC: the endothermic peak started at 121.1 °C upon first heating and peaked at 127.9 °C.

[0170] C18MDIC18

[0171] Under argon atmosphere, 20.2 g MDI, 500 mL dry DCM, and a magnetic stir bar were added to a 1 L dry Schlenk flask. The mixture was stirred in an oil bath at 30 °C to dissolve the MDI. The solution was filtered through a sleeve filter into a 3-necked RBF and brought to 35 °C. Under argon atmosphere, the RBF was fitted with a condenser, a thermocouple was inserted through a diaphragm, and 43.71 g 1-octadecanool was added to the reactor in small increments. After adding half of the alcohol over 9 minutes, 3 drops of pure dibutyltin dilaurate were added, and exothermic reaction was observed. The remaining alcohol was added all at once, along with an additional 250 mL of dry DCM to assist stirring with the stir bar, and the solution was refluxed for 2.5 hours. The slurry was then sampled. The sample was dried under vacuum at 40 °C and 10 mbar to obtain a white solid, which was analyzed by ATR-IR and no residual isocyanate group bands were found. All solids were vacuum filtered on a nonwoven fabric supported by glass frit, washed with fresh DCM to obtain a white powder, which was further rotary evaporated in a wide-mouth flask. 62.25 g of solid white powder was obtained. It was recrystallized in THF at approximately 25% by weight by gentle heating until dissolved and cooling overnight at room temperature. The crystalline solid was vacuum filtered and dried under vacuum at 40 °C to 9 mbar using a rotary evaporator, and further dried under dynamic vacuum on a high-vacuum line at room temperature to 90 mTorr to collect 56.22 g (88.7% yield) of white crystalline solid. Melting point determined by DSC: the endothermic peak started at 127.9 °C upon first heating and peaked at 131.9 °C.

[0172] ODI-BPF-ODI

[0173] Under nitrogen atmosphere, 5.0 g of bisphenol F, a magnetic stir bar, and 14.8 g of stearyl isocyanate, filtered through a 1 μm glass microfiber filter, were added to a dry 100 mL round-bottom flask. A heating mantle was fitted to the flask, and the mixture was stirred until a homogeneous slurry was formed. The mixture was heated to 197 °C and cooled to 78 °C over 1 hour. After sampling, 3 drops of dibutyltin were added, and the mixture was heated to 165.2 °C over 40 minutes and cooled to form a solid. The mixture was then sampled, and the mixture was reheated to 182.6 °C and cooled to room temperature over 1 hour. The solid was sampled and analyzed by ATR-IR, which showed the disappearance of the isocyanate band. A small amount of the product was dissolved in THF at 55 °C (5% by weight) and recrystallized at room temperature for 2 hours. After vacuum filtration and drying under high vacuum, the recovery rate of the recrystallized sample was 80.3%. The melting point of the recrystallized material, as determined by DSC, showed that the initial temperature of the endothermic peak was 128.5℃ and the peak temperature was 142.4℃ during the first heating.

[0174] n -BuPhMDIPh n -This

[0175] Add 3.57 g MDI (mw = 250.25, solid) and 4.3 g 4-n-butylphenol (mw = 150.22) to a round-bottom flask. Assemble the flask with a water condenser connected to a nitrogen inlet. Heat the mixture to approximately 80-120 °C until the solution becomes a clear liquid. Reheat the solution for 1 hour until all the alcohol is consumed. Cool the solution to room temperature, and the product solidifies. Its IR spectrum shows the complete disappearance of the isocyanate group band. Melting point determined by DSC: two endothermic peaks at 140.0 °C and 155.4 °C during the first heating; a single exothermic peak at 124.6 °C during cooling; and a single endothermic peak observed during the second heating, with an onset temperature of approximately 118 °C and a peak temperature of 136.0 °C.

[0176] Preparation of an anti-stick layer comprising organic polymers and anti-stick compounds

[0177] General coating solution preparation procedure

[0178] The organic polymers were mixed separately with the solvents shown to prepare organic polymer solutions having the weight percent solids described in the table. The polymers and solvents were placed in a container and swirl overnight at 80 rpm to obtain stable polymer solutions.

[0179] Add the anti-sticking compound (i.e., the additive) shown to the organic polymer solution in the amounts described in the table, and vortex at high speed for one minute to form a homogeneous solution. Heat the coating solution to ensure that all additives are completely dissolved in each polymer solution.

[0180] Method of applying coating solution to substrate

[0181] Manually apply the coating by scraping: Apply the coating solution to the substrate (e.g., PET, PCK) and use a Mayer bar or a 4" milling / grooving block (Gardco) to pull the solution down along the substrate at a fixed (1-8 mil) gap height. For PET and other rigid substrates, tape them to a flat surface for scraping, but for soft / deformable substrates such as PCK, place them on a vacuum plate to flatten the coating, resulting in a uniform coating when subjected to the weight of the coating block. Drying conditions vary and are described in the table.

[0182] The automated coating methods of the embodiments in Tables 2B, 5, 7, and 8

[0183] The coating solution was supplied to a 4-inch (10.2 cm) wide trough-type coating die and applied to a 6-inch (15.2 cm) wide PCK web moving at a speed of 5 ft / min (1.52 m / min). The solution delivery rate was adjusted to achieve the dry coating thicknesses listed in the table below for each embodiment. The coated web then traveled approximately 13 feet (4 m) before entering a 30-foot (9.14 m) conventional air flotation dryer with three independently controlled zones, each 10 feet (3.05 m) long. The oven zone temperatures for each sample are provided in the table below.

[0184]

[0185] The contact angles of samples prepared by applying a 4-mil gap to a PCK substrate were evaluated, as reported in the table below:

[0186] Hot extrusion examples

[0187] Polypropylene (PP1024) or polyester (PETGN071) was compounded with varying levels of finely powdered C18MDIC18 anti-sticking additive and extruded via a Thermo Technologies Process 11 parallel twin-screw extruder to form films 1 to 1.5” wide and 10 mil thick. The polypropylene or polyester granules and anti-sticking additive were fed at 2.2 psi and extruded at 300 RPM using an 18mm twin-screw extruder with two feeders, with an initial zone temperature of 170°C and a final temperature of 200°C. The extruded films were further heat-treated at 120°C for 3 minutes. The two main surfaces (inner and outer) of the resulting extruded films were laminated with 3M 8403 tape, and the resulting laminated samples were aged at 50°C for 48 hours. Release peel tests were performed on the final samples. The results were summarized.

[0188]

[0189] Using the analytical data described below, the sample surface was examined using X-ray photoelectron spectroscopy (XPS) (also known as analytical chemical electron spectroscopy (ESCA)). This technique provides analysis of the outermost 3 nanometers to 10 nanometers (nm) on the sample surface. Photoelectron spectroscopy provides information on the concentration of elements and chemicals (oxidation states and / or functional groups) present on the solid surface. At detection limits for most substances in the range of 0.1 to 1 atomic percent concentration, this technique can detect all elements in the periodic table except hydrogen and helium.

[0190]

[0191] If the surface has 100% anti-sticking compound, the nitrogen concentration will be 3.39.

[0192] Therefore, the results show that the anti-sticking compound concentrates on the surface.

[0193] NMR and IR analysis

[0194] Through proton nuclear magnetic resonance ( 1 1H NMR analysis of C18MDIC18 and ODI-BPF-ODI: The sample was dissolved in deuterated DMSO in an NMR tube in a 120°C heating block and placed in the ceramic rotator of a Bruker Avance III HD NMR spectrometer with a Bruker 5mm TCI reverse probe. The probe was heated to the set temperature, allowed to equilibrate for 10 minutes, and 1H NMR scans were collected. The temperature was then adjusted to the next set point and data were collected in the same manner.

[0195] As the temperature decreased from 100°C to 25°C, the chemical shift of the proton signal of the urethane group of C18MDIC18 shifted from 9.15 ppm to 9.42 ppm, and the signal narrowed.

[0196] ODI-BPF-ODI exhibits proton signal chemical shifts at 9.11 ppm, 9.05 ppm, and 7.65 ppm at 25 °C. The 7.65 ppm proton peak is attributed to the absence of H bonds in the molecule. As the temperature decreases from 100 °C to 25 °C, the proton signal chemical shifts of the urethane group in ODI-BPF-ODI shift from approximately 8.75 ppm to 9.15 ppm and 9.05 ppm, and the signal narrows.

[0197] For both compounds, the aromatic proton signal of the phenyl group becomes weaker at high fields (shielding effect) and stronger at low fields. These results indicate that, in the gel phase, these compounds possess a self-assembled structure stabilized by hydrogen bonds and contributed to to a small extent by π-π-stacking interactions.

[0198] Infrared spectroscopy analysis was performed using a Nicolet 6700 FTIR system with a Pike GladiATR heating stage containing a diamond ATR crystal. The sample was pressed onto the crystal using an anvil and positioned at a 4 cm⁻¹ angle. -1 Resolution from 4000cm -1 -400cm -1 Collect 16 scans, such as Figure 4 and Figure 5 As shown. Samples are collected under ambient conditions, scanned, then heated to approximately 165°C, scanned again, cooled to approximately 120°C, scanned again, and then heated to approximately 130°C to 140°C to collect a final set of scans. Figure 4 and Figure 5 As shown in the figure. Notably, at room temperature, peak absorbance with peak heights between 0.05 and 0.13 exists in the wavelength range of 3250 nm to 3400 nm. Such peak absorbance is also present after two melting and cooling cycles. This indicates the thermal stability of the compound.

[0199] Additional hot extrusion examples

[0200] Thermoplastic polymers and anti-sticking agents are fed into the extruder hopper from separate feeders at specified feed rates to obtain various anti-sticking agent concentrations (as shown in the table) and / or polymer blends. The compositions are then mixed and heated through a temperature-controlled zone of the twin-screw extruder. For LDPE, LDPE / 878P blends, and PP, the temperature in this zone is increased from 375℉ to 520℉. For PTA Clear 62 / PCTg blends, the temperature in this zone is increased from 400℉ to 520℉. The die temperature is 530℉. The polymer blend is then fed through the die onto a casting wheel (temperature 80℉), where the speed varies depending on the desired coating or film thickness.

[0201] In some embodiments, as shown in the example table, a PCK or PET liner is wound around a casting wheel, allowing the film to be extruded directly onto the liner. Single-sided and double-sided anti-stick liners are prepared by extruding the composition onto PCK and PET substrates. In the double-sided extrusion coating embodiment, the single-extrusion liner is flipped so that the first side contacts the casting wheel, and the next composition is extruded onto the uncoated side of the liner. The contact time of the liner on the casting wheel is very short (seconds).

[0202] Unless otherwise specified, the extruded anti-stick composition has a thickness of approximately 1 mil (25 micrometers). Specific times and temperatures for subsequent heat treatment are detailed in the table below. The results are as follows.

[0203]

[0204] Cross-linked organic polymers

[0205] Table 20A- A two-part composition was prepared by dissolving MDI (15.02 g) and CAPA 3031 (18 g) monomers in THF (218.7 g) and dissolving a separate solution in (1:1 toluene:cyclopentanone weight / weight). Another solution was prepared by adding Desmodur N3390 (30.6 g) and CAPA 3031 (18 g) to toluene (437.2 g) and THF (50.0 g). In the first embodiment below, the solutions were combined (10 g each at a 1:1 weight ratio) and coated after adding one drop of dibutyltin dilaurate (50 wt% in THF) and mixing. In the second embodiment, the MDI / CAPA solution from toluene / cyclopentanone was coated after adding one drop of dibutyltin dilaurate (50 wt% in THF) and mixing. The coating was prepared on PET with a 6-mil wet gap. The wet coating was dried in a forced-ventilation oven on an aluminum tray at 140°C for 15 minutes, during which time MDI and CAPA reacted to form polyurethane. The dried sample was then aged in a forced-ventilation oven. The sample was evaluated using 3M 8403.

[0206]

[0207] Table 20B - A two-part composition was prepared by adding Desmodur N3390 (30.6 g) and CAPA3031 (18 g) to toluene (437.2 g) and THF (50.0 g). The solution was coated after adding one drop of dibutyltin dilaurate (50 wt% in THF) and mixing it into approximately 20 g of the coating solution. A coating was prepared on the glossy surface of the PCK with a 5 mil wet gap. The wet coating was dried in a forced-air oven on an aluminum tray at 120 °C for 15 minutes, during which time Desmodur and CAPA reacted to form polyurethane. The dried sample was then aged in a forced-air oven. The sample was evaluated using 3M 8403.

[0208]

[0209] Table 21 A 5% by weight solution of C18MDIC18 in 85 / 15 toluene / IPA organic solvent, consisting of 3110M and 3pph (based on the amount of 3110M), was coated onto PET and PCK substrates, followed by overnight aging of the laminated 3M 8403 tape at 50°C.

[0210]

[0211] Table 22A 10% by weight solution of -D1102 SBS and 3pph (based on the amount of D1102) of C18MDIC18 was applied to PET and PCK substrates to form a coating thickness of 4 mils, followed by overnight aging of the laminated 3M 8403 tape at 50°C.

[0212]

[0213] Table 25A - UV-cured D1102 SBS

[0214] 10% by weight of D1102 dissolved in an organic solvent (80 / 20 toluene IPA) was coated onto PET and PCK substrates at a thickness of 4 micrometers, followed by overnight aging of the laminated 3M 8403 tape at 50°C. The dried coating (approximately 0.4 micrometers) was cured by four irradiations with H lamps using a nitrogen-inert Heraeus DRS 61100N conveyor system with a Light Hammer 6 UV source from Fusion UV Systems, Inc.

[0215]

[0216] D1102-crosslinked with C18MDIC18 relative to uncrosslinked

[0217] Prepare a D1102 SBS solution at 10 wt% in 80 / 20 toluene / IPA, heating and stirring at 80°C until dissolved. Separate the room temperature solution and mix it only with 3 pphr of C18MDIC18, or with 3 pphr of C18MDIC18, 2 pphr of PETMP, and 2 pphr of ACHN. Heat the solution at 65°C in a dry thermostat, stirring occasionally, until glossy. Add 1 g of sample aliquots to 4 oz wide-mouth flasks and dry in a forced-ventilation oven at 120°C for 40 minutes. Peel the dried sample from the bottom of the flask and add it to vials, completely immersing them in 20 g of 80 / 20 toluene / IPA (wt / wt) at room temperature.

[0218] The sample containing C18MDIC18 and without crosslinking agent (approximately 5% by weight solid solution) completely lost its membrane structure within 10 minutes and dissolved completely with further gentle stirring. The samples containing C18MDIC18, PETMP, and ACHN retained their membrane structure even after 24 hours and did not dissolve with gentle stirring.

Claims

1. An adhesive article, said adhesive article comprising: Substrate; An anti-stick layer disposed on the substrate, the anti-stick layer comprising an organic polymer and an anti-stick compound; The anti-sticking compound has the following formula: in X is -CH2-; L is a divalent linker containing a carbamate moiety; and R1 and R2 independently contain C4-C30 hydrocarbon groups; and An adhesive that is bonded to the release layer.

2. The adhesive article according to claim 1, wherein R1 or R2 independently contains at least 10 carbon atoms or at least 12 carbon atoms.

3. The adhesive article according to claim 1, wherein R1 or R2 contains at least 18 carbon atoms.

4. The adhesive article according to claims 1 to 3, wherein the anti-adhesive compound has the following formula: 。 5. The adhesive article according to claims 1 to 3, wherein the anti-adhesive compound has the following formula: 。 6. The adhesive article according to claims 1 to 5, wherein the anti-adhesive layer comprises 0.5% to 10% by weight of the anti-adhesive compound.

7. The adhesive article according to claims 1 to 6, wherein the anti-adhesive layer comprises a first main surface near the substrate and a second main surface near the adhesive, wherein the second main surface contains an anti-adhesive compound at a higher concentration than the first main surface.

8. The adhesive article according to claims 1 to 7, wherein the organic polymer has a melting temperature or glass transition temperature in the range of 150°C to 450°C.

9. The adhesive article according to claims 1 to 8, wherein the organic polymer is soluble in an organic solvent at a concentration of 10% by weight, said organic solvent being selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, cyclopentanone, 2-butanone, xylene, 2-propanol, n-propanol, methanol, and mixtures thereof.

10. The adhesive article according to claims 1 to 9, wherein the anti-adhesive compound is soluble or dispersed in an organic solvent at a concentration of 10% by weight, said organic solvent being selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, cyclopentanone, 2-butanone, xylene, 2-propanol, n-propanol, methanol, and mixtures thereof.

11. The adhesive article according to claims 1 to 10, wherein the organic polymer is amorphous.

12. The adhesive article according to claims 1 to 11, wherein the organic polymer comprises a polyolefin polymer.

13. The adhesive article according to claims 1 to 12, wherein the anti-adhesive compound has a melt temperature in the range of 95°C to 150°C.

14. The adhesive article according to claims 1 to 13, wherein the substrate comprises an organic polymer, paper, or a combination thereof.

15. The adhesive article according to claims 1 to 14, wherein the anti-adhesive layer has a static contact angle characteristic selected from the following: a) The static contact angle with diiodomethane is 45 to 85 degrees; b) The static contact angle with n-hexadecane is 35 to 55 degrees; and c) The static contact angle with dimethylsiloxane is 20 to 40 degrees.

16. The adhesive article according to claims 1 to 15, wherein the adhesive is a pressure-sensitive adhesive.

17. The adhesive article according to claims 1 to 16, wherein the adhesive is a silicone adhesive.

18. The adhesive article according to claims 1 to 17, wherein the adhesive exhibits a peel adhesion force to the release layer that is at least 25% less than a peel adhesion force to a substrate without the release layer.

19. The adhesive article according to claims 1 to 18, wherein the anti-adhesive compound forms a molecular assembly structure.

20. The adhesive article according to claims 1 to 19, wherein the organic polymer comprises unsaturated groups.

21. The adhesive article according to claim 20, wherein the unsaturated group is an olefin or alkenyl group.

22. The adhesive article according to claims 1 to 21, wherein the organic polymer is polyurethane.

23. The adhesive article of claim 22, wherein the polyurethane is a reaction product of a polyisocyanate and / or polyol comprising at least three isocyanate groups and / or -OH groups.

24. The adhesive article according to claims 1 to 23, wherein the organic polymer is crosslinked.

25. The adhesive article of claim 23, wherein the organic polymer is crosslinked with a chemical crosslinking agent or crosslinked by exposure to photochemical radiation.

26. The adhesive article according to claims 24 to 25, wherein the crosslinked organic polymer is insoluble in organic solvents at a concentration ranging from 5% to 10% by weight of solids.

27. An adhesive article comprising anti-stick coatings disposed on two main surfaces of a substrate, wherein at least one of the anti-stick coatings is an anti-stick layer according to claims 1 to 26.

28. An anti-stick padding article, the anti-stick padding article comprising: Substrate; An anti-adhesion layer disposed on the substrate, the anti-adhesion layer comprising an anti-adhesion compound; wherein the anti-adhesion compound has the following formula: in X is -CH2-; L is a divalent linker containing a carbamate moiety; and R1 and R2 independently contain C4-C30 hydrocarbon groups.

29. The anti-stick pad article of claim 19, wherein the anti-stick layer further comprises an organic polymer.

30. The anti-stick pad according to claims 28 to 29, wherein the anti-stick layer is further characterized by claims 2 to 27.

31. A composition comprising an organic polymer and a compound having the following formula: in X is -CH2-; L is a divalent linker containing a carbamate moiety; and R1 and R2 independently contain C4-C30 hydrocarbon groups.

32. The composition according to claim 31, wherein the composition is further characterized by claims 2 to 27.

33. A membrane or membrane layer comprising the composition according to claims 31 to 32, wherein the compound is uniformly distributed within the organic polymer or concentrated on the surface of the membrane or membrane layer.

34. A method for preparing a composition, the method comprising: Combining organic polymers with compounds having the following formula: Where L is a divalent linker containing a carbamate moiety; and R1 and R2 are independently C4-C22 hydrocarbon groups.

35. The method of claim 34, further comprising applying the composition to a substrate.

36. The method according to claims 34 to 35, wherein combining the organic polymer and the compound comprises forming a solution of the organic polymer, the compound, and an organic solvent.

37. The method according to claims 34 to 36, wherein the organic solvent is selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, cyclopentanone, 2-butanone, xylene, 2-propanol, and mixtures thereof.

38. The method according to claims 34 to 37, further comprising removing the organic solvent.

39. The method according to claims 34 to 35, wherein combining and applying the organic polymer and the compound comprises thermal extrusion.

40. The method of claim 39, wherein the substrate is a thermoplastic organic polymer co-extruded with the composition.

41. The method according to claims 34 to 40, further characterized by claims 2 to 27.

42. The method according to claims 35 to 41, comprising the organic polymer and compound to which heat treatment is applied.

43. The method according to claims 34 to 42, further comprising exposing the applied organic polymer and compound to heat, photochemical radiation, or a combination thereof to crosslink the organic polymer.

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