Composition and thermosetting adhesive film derived from the composition

Abstract

A composition and a thermosetting adhesive film obtained therefrom. The thermosetting adhesive film can be activated at low temperatures (below 100°C, preferably 60°C to 80°C), and once cured, it is self-supporting and exhibits excellent adhesive strength.

Description

Technical Field

[0001] The present invention relates to a composition and a thermosetting adhesive film derived from the composition. In particular, a thermosetting adhesive film that can be activated at a low temperature (less than 100°C, preferably 60°C to 80°C) has self-supporting properties during curing and exhibits excellent adhesive strength.

Background Art

[0002] Thermosetting adhesive films are widely used in the production of films for substrate assembly. The term "thermosetting" (or "thermally activatable") means that the composition has the potential adhesive property of being activated only after being heated to a predetermined temperature or higher. Such thermosetting compositions have the advantages of being easier and quicker to use compared to solvent-based adhesives, such as the need for evaporation of solvents in solvent-based adhesives. In the manufacturing process, the thermosetting adhesive film is placed between the surfaces of the substrates to be assembled and brought into contact with the substrates while heating to activate the adhesive composition. The heating time varies depending on the thickness of the substrate, but it should not be too long to avoid thermal deformation of the substrate. After cooling, an adhesive layer having a certain adhesive strength for assembling the substrates is obtained.

[0003] Conventional thermosetting adhesive films disclosed in the prior art or existing in the market are based on polyols and NCO-terminated isocyanates. It has been observed that such adhesives exhibit very high activation temperatures (above 160°C). To fully exhibit the adhesive properties, it is necessary to heat to a very high temperature. If this cannot be done, the adhesive performance will be insufficient and effective adhesion to the substrate cannot be provided. However, some substrates, such as polyolefins and polypropylenes, deteriorate when heated above 160°C. On the other hand, in some cases, it has been observed that the adhesive strength is not sufficient even after the adhesive film has cured.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Considering the above, there is a need for a thermosetting adhesive film that can be activated at low temperatures (below 100°C, preferably 60°C to 80°C), self-supports during curing, and exhibits excellent adhesive strength. [Means for solving the problem]

[0005] Summary of the Invention According to a first aspect of the present invention, a composition comprising the following is disclosed herein: (A) At least one thermoplastic polymer having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less. (B) At least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, (C) At least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, and (D) At least one organic solvent present in an amount of more than 36% to 95% based on the total weight of the composition.

[0006] According to a second aspect of the present invention, a method for preparing a thermosetting adhesive film derived from a composition according to the present invention is provided.

[0007] According to a third aspect of the present invention, a thermosetting adhesive film derived from a composition according to the present invention is provided.

[0008] According to a fourth aspect of the present invention, an article is provided comprising a first substrate, a second substrate, and a thermosetting adhesive film according to the present invention disposed between the first substrate and the second substrate.

[0009] A fifth aspect of the present invention provides the use of a composition according to the present invention or a thermosetting adhesive film or thermosetting adhesive film article according to the present invention in the manufacture of automotive parts, truck bed covers, textile laminations, assemblies, and electronic equipment.

[0010] Other characteristics and aspects of the protected items will be described in more detail below.

[0011] Detailed description of the present invention Those skilled in the art will understand that this invention is merely a description of exemplary embodiments and is not intended to limit broader embodiments of the invention. Each embodiment described herein may be combined with one or more other embodiments unless expressly otherwise indicated. In particular, features indicated as preferred or advantageous may be combined with one or more other features indicated as preferred or advantageous.

[0012] Unless otherwise specified, terms used in the context of this invention shall be interpreted according to the following definitions.

[0013] Unless otherwise specified, the terms "a," "an," and "the" used herein include both singular and plural forms.

[0014] As used herein, the terms “comprising” and “comprises” are synonymous with “including,” “includes,” or “contains,” and are comprehensive or open-ended, not excluding any additional, undescribed members, elements, or process steps.

[0015] In this specification, the terms “at least one” or “one or more” used to define components refer to the types of components, not the absolute number of molecules. For example, “one or more polyols” means one type of polyol or a mixture of several different polyols.

[0016] The term "thermosetting" (or "thermally activatable") is understood to mean that the adhesive film has potential adhesive properties that are only activated after heating the film above a predetermined temperature (the "activation temperature"). The adhesive properties of the film are manifested during this thermally activated stage.

[0017] The term "adhesive film" means an adhesive in the form of a film.

[0018] The term "polyurethane" also means polyurethanes, as well as polyurethanes containing urea groups in the backbone of the polyurethane.

[0019] As used herein, the term "room temperature" refers to a temperature of about 20°C to about 25°C, preferably about 25°C.

[0020] Unless otherwise specified, the recitation of numerical endpoints includes not only the recited endpoints but also all numbers and fractions included within each range.

[0021] All references cited herein are hereby incorporated by reference in their entirety.

[0022] Unless otherwise specified, the molecular weight refers to the number average molecular weight (Mn). All molecular weight data refers to values obtained by gel permeation chromatography (GPC) unless otherwise specified (e.g., in accordance with DIN 55672).

[0023] The softening point referred to herein is determined using the ring and ball method in accordance with DIN ISO 4625.

[0024] Unless otherwise defined, all terms (including technical and scientific terms) used in this invention have the meaning commonly understood by those of ordinary skill in the art to which this invention pertains.

[0025] In one aspect, the present disclosure generally is as follows: (A) At least one thermoplastic polymer having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimum activation temperature of 100 °C or less, (B) At least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, (C) At least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, and (D) At least one organic solvent, and the organic solvent is present in an amount of more than 36% to 95% based on the total weight of the composition The present invention relates to a composition containing the above.

[0026] (A) Thermoplastic polymer According to the present invention, the composition contains (A) at least one thermoplastic polymer having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimum activation temperature of 100 °C or less.

[0027] The thermoplastic polymer (A) provides the skeleton of the thermosetting adhesive film derived from the composition. Without such a thermoplastic polymer (A), the thermosetting adhesive film obtained from the composition cannot realize a self-supporting adhesive film.

[0028] Unlike a thermosetting polymer that solidifies by cross-linking or curing when exposed to heat and / or an appropriate curing agent, a thermoplastic polymer is flexible at high temperatures and solidifies when cooled.

[0029] The term "optimum activation temperature" described in the present specification means the temperature range (or temperature point) of the thermoplastic polymer in which (physically) aggregation occurs, has sufficient strength, and the non-aggregation rate is less than 10%. The optimum activation temperature of the thermoplastic polymer described in the present specification can be determined according to EN 12961:2001.

[0030] In preferred embodiments, the optimal activation temperature of component (A) is less than 85°C, preferably 30°C to less than 80°C, more preferably 30°C to less than 70°C, and even more preferably 30°C to less than 60°C. Within this preferred range, the thermosetting adhesive film obtained from the composition can be self-supporting upon curing and exhibit a certain level of adhesive strength.

[0031] Generally, the thermoplastic polymers described herein are chemically nonreactive and, upon heating, undergo aggregation, becoming a flexible state with certain adhesive properties. In some embodiments, the thermoplastic polymer may contain hydroxyl groups that can react with component (C).

[0032] In the present invention, widely known thermoplastic polymers can be used as long as the molecular weight and optimal activation temperature are satisfied. Suitable thermoplastic polymers used in the present invention can be selected from the group consisting of thermoplastic polyurethane polymers, polyester polymers, acrylic polymers, ethylene-vinyl acetate copolymers, styrene block copolymers, polyvinyl acetol, styrene acrylonitrile, polyolefins, polyacrylonitrile, ethylene vinyl acetate terpolymers, functionalized ethylene vinyl acetate, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene butadiene copolymers and / or block copolymers, and are preferably selected from thermoplastic polyurethane polymers, polyester polymers, acrylic polymers, styrene block copolymers, and combinations thereof.

[0033] A thermoplastic polyurethane polymer used as component (A), having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less, can be obtained from a ring-opening polymerization reaction of a lactone such as ε-caprolactone, or a polyester polyol and / or polyether polyol with a diisocyanate. Optionally, such a component can also be obtained from a further reaction with a chain extender such as a low molecular weight polyol, preferably a diol, or a diamine that forms a urea bond.

[0034] Useful polyester polyols used in the production of thermoplastic polyurethane polymers include, for example, polyester polyols derived from linear dicarboxylic acids, derivatives of dicarboxylic acids (e.g., anhydrides, esters, and acid chlorides), aliphatic polyols, alicyclic polyols, linear polyols, branched polyols, and combinations thereof. Useful dicarboxylic acids that serve as raw materials for polyester polyols include adipic acid, succinic acid, sebacic acid, dodecanediol, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, and combinations thereof. Useful aliphatic diols that serve as raw materials for polyester polyols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and combinations thereof.

[0035] Useful polyether polyols used in the production of thermoplastic polyurethane polymers are obtained from the polymerization of cyclic oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, or by adding one or more such oxides to a polyfunctional initiator having at least two active hydrogens, such as water, a polyhydric alcohol (e.g., ethylene glycol, propylene glycol, diethylene glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, pentaerythritol, bisphenol A), ethylenediamine, propylenediamine, triethanolamine, and 1,2-propanedithiol.

[0036] Useful thermoplastic polyurethane polymers (A) generally consist of a soft segment, such as a polyether or polyester polyol, and a hard segment, usually obtained from the reaction of a low molecular weight diol with a diisocyanate. Commercially available thermoplastic polyurethane polymers used as component (A) include, but are not limited to, the Pearlstick series from Lubrizol, such as 5707, 5703, 5701, 5714, 5713, 5715, 45-40 / 05 TPU, 45-40 / 11STPU, 45-40 / 27TPU, and 45-60 / 08; the HF-4003LH, 3003EH series, HF-3H, and 6H series from Huafeng Chemicals; and the WHT-61, 63, 64, 65, and 67 series from Wanhua Chemicals.

[0037] The polyester polymer used as component (A), having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less, contains at least one polyester diol, such as ethylene glycol, diethylene glycol, trimethylene glycol, butanediol (1,4-butanediol; 1,2-butanediol; 1,3-butanediol), neopentyl glycol, 2-methyl-1,3-propanediol, hexanediol (hexamethylene glycol), propanediol (propane-1,2-diol, propane-1,3-diol or propylene glycol), trimethylene These can be obtained by polycondensation of chloropropane, cyclohexanedimethanol, or a combination thereof with at least one dicarboxylic acid or its ester or anhydride derivative, such as terephthalic acid, dimethyl terephthalate, isophthalic acid, adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, dodecanoic acid (1,10-decanedicarboxylic acid), succinic acid, phthalic anhydride, maleic anhydride, and hydroxycarboxylic acids, such as diesters obtained from polycaprolactone or ε-caprolactone, and diethylene glycol, or a combination thereof. Commercial polyester polymers used as component (A) include, but are not limited to, TOYOBO's BX 1001, Perstorp's CAPA® 6800, 6500, 6400, Daicel's PLACCEL H series, and Hunan Juren Chemical's PCL65000, PCL68000.

[0038] Acrylic polymers used as component (A) having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less can be obtained by polymerizing esters of acrylic acid and methacrylic acid monomers. Exemplary useful monomers used to synthesize component (A) include soft monomers such as ethyl acrylate, 2-ethylhexyl acrylate, and n-butyl acrylate, and hard monomers such as methyl methacrylate and isobutyl acrylate. Exemplary acrylic polymers used as component (A) include polymethyl methacrylate, n-butyl acrylate-based block copolymers, n-butyl acrylate / 2-ethylhexyl acrylate-based block copolymers, and combinations thereof. It is preferable to use acrylic block polymers derived from both soft monomers and hard monomers. Commercially available acrylic polymers used as component (A) include, but are not limited to, n-butyl acrylate-methyl methacrylate copolymer under the trade name Kuraray™ LA2140, manufactured by SANYO.

[0039] The styrene block copolymer used as component (A), having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less, comprises aromatic vinyl polymer blocks and saturated intermediate blocks, preferably hydrogenated conjugated diene polymer blocks, or unsaturated intermediate blocks. The blocks can be arranged in various configurations, such as linear, branched, radial, star-shaped, and combinations thereof. Aromatic vinyl polymer blocks can be derived from a variety of aromatic vinyl compounds, such as styrene, alpha-methylstyrene, beta-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene-2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, 1,3-vinylnaphthalene, vinylanthracene, indene, acenaphthylene, and combinations thereof. Hydrogenated diene polymer blocks can be derived from a variety of diene-containing compounds, including, for example, isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and combinations thereof. Useful styrene block copolymers having a saturated intermediate block as component (A) include, for example, triblock, multi-arm, and radial copolymers, including styrene-ethylene / butene-styrene (SEBS), styrene-ethylene / propylene-styrene (SEPS), styrene-ethylene-ethylene / propylene-styrene (SEEPS), styrene / isobutylene / styrene (SIBS), and combinations thereof. Useful styrene block copolymers having an unsaturated intermediate block as component (A) include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene-isobutylene-styrene (SBBS), styrene-isoprene-butadiene-styrene (SIBS), and combinations thereof. Examples of commercially available styrene block copolymers that can be used as component (A) include, but are not limited to, Kuraray's HYBRAR® 5125 and 7311.

[0040] The ethylene-vinyl acetate copolymer used as component (A), having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less, is a copolymer derived from at least one ethylene monomer and at least one vinyl acetate monomer. From the viewpoint of the strength and flexibility of the adhesive film obtained from the composition, it is preferable that the ethylene-vinyl acetate copolymer used as component (A) has a vinyl acetate content of 65% by mass or more. Examples of commercially available ethylene-vinyl acetate copolymers used as component (A) include, but are not limited to, Levamelt® 686 (68% by weight vinyl acetate) manufactured by ARLANXEO, and KBE-68 A and KBE-68 B manufactured by Kuraray.

[0041] Other useful thermoplastic polymers having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less include, but are not limited to, polyvinyl acetol, styrene acrylonitrile, polyolefins, polyacrylonitrile, ethylene vinyl acetate terpolymer, functionalized ethylene vinyl acetate, ethylene acrylate copolymer, ethylene acrylate terpolymer, ethylene butadiene copolymer and / or block copolymer, and combinations thereof.

[0042] The above thermoplastic polymers may be used individually or in combination of two or more. When at least two thermoplastic polymers are used as component (A), their respective molecular weights and optimal activation temperatures must fall within the requested range.

[0043] In preferred embodiments, the number-average molecular weight of the thermoplastic polymer is 10,000 to 200,000 g / mol, preferably 8,000 to 150,000 g / mol, and more preferably 20,000 to 100,000 g / mol.

[0044] Particularly preferably, component (A) may be present in an amount of 1% to 95% by weight, preferably 10% to 40% by weight, based on the total weight of the composition.

[0045] (B) Polyester polyol According to the present invention, the composition comprises at least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, which reacts with component (C) described later to form an effective bond when exposed to heat.

[0046] Component (B) useful in the present invention includes those having at least two hydroxyl groups, for example three or four hydroxyl groups, in one molecule, and having an aromatic group in the molecule, and the hydroxyl value is preferably in the range of 10 mg KOH / g or more, preferably 15 mg KOH / g or more, more preferably 20 to 90 mg KOH / g, and even more preferably 30 to 60 mg KOH / g.

[0047] Component (B) used in the present invention is preferably solid at room temperature (20°C). In some embodiments, component (B) can be selected from amorphous polyester polyols, semicrystalline polyester polyols, crystalline polyester polyols, and combinations thereof, and from the viewpoint of solubility in organic solvents, amorphous polyester polyols, semicrystalline polyester polyols, and combinations thereof are preferred.

[0048] As used herein, the term "amorphous polyester polyol" means a polyester polyol that does not exhibit a melt transition when measured using differential scanning calorimetry (DSC) and does not have a crystalline form. It is preferable to have a degree of crystallinity of less than 10% by weight, preferably less than 5%, advantageously less than 2%, and more advantageously less than 1%.

[0049] The term "semicrystalline polyester polyol" refers to a polyester polyol whose structure contains both crystalline and amorphous regions. It is preferable that it has a degree of crystallinity of at least 20% to less than 80% by weight, preferably at least 30% to less than 80%, and preferably at least 40% to less than 80%.

[0050] As used herein, the term "crystalline polyester polyol" means a polyester polyol that has a melt transition and a crystalline form when measured using differential scanning calorimetry (DSC). It is preferable that it has a degree of crystallinity of at least 80%, preferably at least 90%, by weight.

[0051] Crystallinity, which indicates the proportion of a substance in a crystalline state, can be determined by X-ray diffraction analysis at various angles of incidence, calorimetry such as DSC (differential scanning calorimetry), or other techniques that can estimate the proportion of the crystalline phase in semi-crystalline polyester polyols.

[0052] In the present invention, examples of amorphous polyester polyols useful as component (B) include reaction products of polyacid components (e.g., polyacids, polyacid anhydrides, polyacid esters, and polyacid halides) with a stoichiometrically excess polyol. At least one of the polyacid component and the polyol contains an aromatic group. Suitable polyacids include, for example, diacids (e.g., dicarboxylic acids), triacids (e.g., tricarboxylic acids), and higher-order acids, such as aromatic dicarboxylic acids, their anhydrides and esters (e.g., terephthalic acid, isophthalic acid, dimethyl terephthalate, diethyl terephthalate, phthalic acid, phthalic anhydride, methyl-hexahydrophthalic acid, methyl-hexahydrophthalic anhydride, methyl-tetrahydrophthalic acid, and methyl-tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and tetrahydrophthalic acid), aliphatic dicarboxylic acids and their anhydrides (e.g., maleic acid, maleic anhydride, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid, decanedicarboxylic acid, octadecanedicarboxylic acid, dimeric acid). Examples include fatty acids, dimerized fatty acids, trimeric fatty acids, and fumaric acid, and alicyclic dicarboxylic acids (e.g., 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid), and mixtures thereof.Examples of suitable polyols include aliphatic polyols, e.g., ethylene glycol, propanediols (e.g., 1,2-propanediol and 1,3-propanediol), butanediols (e.g., 1,3-butanediol, 1,4-butanediol, and 1,2-butanediol), 1,3-butenediol, 1,4-butenediol, 1,4-butynediol, pentanediol (e.g., 1,5-pentanediol), pentenediol, pentynediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Examples include polyethylene glycol, propylene glycol, polypropylene glycol (e.g., dipropylene glycol and tripropylene glycol), 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, dimergol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, glycerol, tetramethylene glycol, polytetramethylene glycol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, trimethylolpropane, pentaerythritol, sorbitol, glucose, and combinations thereof.

[0053] Specific examples of useful amorphous polyester polyols include poly(hexanediol phthalate) polyol, poly(neopentyl glycol adipate) polyol, poly(neopentyl glycol phthalate) polyol, poly(neopentyl glycol hexadiol phthalate) polyol, poly(diethylene glycol phthalate) polyol, poly(ethylene glycol adipate terephthalate) polyol, polyethylene terephthalate polyol, random copolymer diols of ethylene glycol, hexanediol, neopentyl glycol, adipic acid, and terephthalic acid, and combinations thereof.

[0054] When using a solid amorphous polyester polyol, its softening point is preferably 130°C or lower, more preferably 120°C or lower, and more preferably 105°C or lower, for example, 60°C, 80°C, or 100°C, in order to achieve good adhesive strength upon complete curing and to allow for easy dissolution in the composition.

[0055] Suitable crystalline polyester polyols as component (B) in the present invention can be obtained by ring-opening polymerization of lactones such as ε-caprolactone, and / or can be derived from diols and diacids. Examples of diols useful for preparing preferred polyester polyols include ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and combinations thereof. Examples of diacids useful for preparing preferred polyester polyols include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and 1,12-dodecanediol, dimer acids, and combinations thereof. The range of useful diacids includes various diacid derivatives such as carboxylic acid esters (especially methyl and ethyl esters), acid halides (e.g., acid chlorides), and acid anhydrides, as well as combinations thereof.

[0056] Specific examples of suitable crystalline polyester polyols include poly(hexanediol adipate) polyol, poly(butanediol adipate) polyol, poly-epsilon-caprolactone polyol, poly(hexadioldecanediic acid) polyol, poly(hexanediol adipate terephthalate) polyol, and combinations thereof.

[0057] The above polyester polyols may be used individually or in combination of two or more. When at least two types of polyester polyols are used in the composition, their respective weight-molecular weights shall fall within the claimed range.

[0058] Suitable commercially available polyester polyols (B) include FZPE-A03130 from GUANGZHOU FTRT CHEMICAL CO., LTD, DYNACOLL 7110, 7130, 7140, and 7150 from Evonik Industries AG, and FLP PA-1000N from Xuchuan Chemical (Sushow) Co., Ltd.

[0059] Particularly preferably, component (B) may be present in an amount of 0.01% to 80%, preferably 5% to 40%, based on the total weight of the composition.

[0060] (C) Polyisocyanate According to the present invention, the composition comprises (C) at least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule.

[0061] A useful polyisocyanate (C) that can be used in accordance with the present invention is given by the following formula (I): [ka] [In the formula, -R is a divalent group consisting of 6 to 13 carbon atoms. -n is an integer in the range of 0 to 10. It corresponds to this. Preferably, R is a divalent aromatic group or a polyvalent aromatic group, and more preferably a group obtained from an aromatic diisocyanate such as toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI).

[0062] Examples of polyisocyanates (C) that can be used according to the present invention are those of the following formula (I-1) or (I-2): [ka] It corresponds to one of them.

[0063] Preferably, the polyisocyanate (C) that can be used according to the present invention has an NCO content (indicated as %NCO) in the range of 15% to 40% by weight, more preferably 20% to 35% by weight, relative to the weight of the polyisocyanate.

[0064] Preferably, the NCO / OH molar ratio composition is in the range of 0.1 to 8. The isocyanate groups are contributed by component (C) present in the composition according to the present invention, and the hydroxyl groups are contributed by component (B) according to the present invention, and a small amount of hydroxyl groups in component (A) if present. As long as the above molar ratio is satisfied, the weight ratio of polyester polyol (B) to polyisocyanate (C) is not particularly limited.

[0065] Suitable commercially available polyisocyanates (C) are sold as Grilbond® A2bond (MDI uretdione) by EMS-Griltech and Addolink® TT (TDI uretdione) by Rhein Chemie.

[0066] Particularly preferably, component (C) may be present in an amount of 0.05% to 20% by weight, preferably 0.5% to 5% by weight, based on the total weight of the composition.

[0067] (D) Organic solvents According to the present invention, the composition comprises (D) at least one organic solvent, the organic solvent present in an amount of more than 36% to 95% by weight, preferably 50% to 85% by weight, based on the total weight of the composition.

[0068] The organic solvent (D) that can be used according to the present invention is preferably one in which components (A) and (B) and any other components or additives dissolve in the organic solvent (D) to form a mixture, and component (C) can be uniformly dispersed in the mixture.

[0069] Preferably, the organic solvent (D) has a solubility parameter delta (δ) (Hildebrand's solubility parameter, also known as HSP) of 6.9 to 10.0 (cal / cm³).3 ) 1 / 2 The range is such that the hydrogen bonding index (HBI) gamma (γ) is in the range of 5.0 to 7.7. These parameters are defined in a manner well known in the literature, for example, in sections 38 and 39 of patent application US 2004 / 0204524: - The solubility parameter delta is defined in Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Solubility parameters", pp. 361-365; - The hydrogen bonding index represents the ability of solvent molecules to form hydrogen bonds. Donor solvents have a negative hydrogen bonding index, and acceptor solvents have a positive hydrogen bonding index. The hydrogen bonding index is determined according to the deviation of the infrared band of the RO-H stretching band (RC Nelson, RW Hemwall, GD Edwards, Journal of Paint Technology, "Treatment of hydrogen bonding in predicting miscibility", Vol. 42, No. 550, 1970, pp 636-43).

[0070] Preferably, the organic solvent (D) is selected from the group consisting of ketones, preferably aliphatic ketones, and more preferably from the group consisting of acetone, methyl ethyl ketone (MEK), 2-pentanone, 3-pentane, methyl isobutyl ketone, ethyl acetate, and combinations thereof.

[0071] Preferably, the organic solvent (D) has a boiling point below the optimal activation temperature of the thermoplastic polymer (A), for example, below 100°C, more preferably below 80°C, so that the organic solvent can be evaporated without activating the thermoplastic polymer (A) to form a thermosetting adhesive film.

[0072] The above component (D) can be used alone or in combination of two or more components.

[0073] composition Furthermore, the composition according to the present invention may or may not contain at least one optional component selected from polyols (e.g., polyether polyols), silanes, pigments (e.g., carbon black), defoamers, leveling agents, stabilizers (antioxidants, UV stabilizers, heat stabilizers), catalysts, dyes, and mixtures thereof, as long as it does not alter the advantageous properties of the composition according to the present invention.

[0074] The composition according to the present invention may further contain 1% to 10% by weight of at least one of the additives defined above.

[0075] In a particularly preferred embodiment, the composition is based on the total weight of the composition: (A) At least one thermoplastic polymer having a weight molecular weight (Mw) of 10,000 g / mol or more, in an amount of 1% to 95% by weight, preferably 10% to 40% by weight, and exhibiting an optimal activation temperature of 100°C or less, preferably less than 85°C, preferably 30°C to less than 80°C, more preferably 30°C to less than 70°C, and even more preferably 30°C to less than 60°C. (B) At least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, in an amount of 0.01% to 80% by weight, preferably 5% to 40% by weight. (C) At least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, in an amount of 0.05% to 20% by weight, preferably 0.5% to 5% by weight, and (D) At least one organic solvent in an amount of more than 36% by weight to 95% by weight, preferably 50% to 85% by weight. Includes.

[0076] Thermosetting adhesive film and method for manufacturing the same According to a second aspect of the present invention, the present invention relates to a method for preparing a thermosetting adhesive film obtained from the above composition, the method comprising the following steps: 1) A step of preparing a composition according to the present invention by dispersing component (C) in a mixture comprising at least one component (A), at least one component (B), at least one component (D) and any component or additive as defined above; Depending on the circumstances, 1a) a step of applying the composition obtained in step 1) onto a removable liner; and 2) A step to remove component (D) from the composition obtained in step 1) or step 1a). Includes.

[0077] In step 1), before introducing component (C), components (A), (B), and any component or additive are dissolved in an organic solvent (D) with rapid stirring, preferably under high-temperature conditions, for example, at a temperature of 75°C or lower, preferably 65°C or lower. Then, component (C) is added at room temperature to obtain a homogeneous mixture or homogeneous dispersion.

[0078] In some embodiments, the removable liner used in step 1a) has a non-adhesive surface to which the composition is applied. Specifically, the composition is applied as a uniform layer to the non-adhesive surface of the removable liner, such as a silicone-treated surface. The application can be carried out using a film applicator or a bar coater, in particular. Upon completion of steps 1), 1a) and 2), a thermosetting adhesive film in single-layer form is advantageously obtained.

[0079] The apparatus used for mixing, stirring, and dispersion in this process is not particularly limited. Automatic mortars equipped with stirrers and heating devices, Henschel mixers, three-roll mills, ball mills, planetary mixers, bead mills, etc., can be used. These apparatuses may also be used in appropriate combinations. The method for producing the composition is not particularly limited, as long as the above components are uniformly mixed.

[0080] According to a third aspect, the present invention relates to a thermosetting adhesive film obtained by a method according to the present invention.

[0081] According to the present invention, the thermosetting adhesive film is (A) At least one thermoplastic polymer in an amount of 1% to 95% by weight, preferably 30% to 90% by weight, having a molecular weight (Mw) of 10,000 g / mol or more, and exhibiting an optimal activation temperature of 100°C or less, preferably less than 85°C, preferably 30°C or more and less than 80°C, more preferably 30°C or more and less than 70°C, and even more preferably 30°C or more and less than 60°C. (B) At least one polyester polyol having a molecular weight (Mw) of less than 10,000 g / mol, in an amount of 0.01% to 80% by weight, preferably 10% to 50% by weight. (C) At least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, in an amount of 0.1% to 20% by weight, preferably 1% to 10% by weight, and (D) At least one organic solvent in an amount of less than 2.0% by weight, preferably less than 0.5% by weight, and more preferably less than 0.1% by weight. Includes, All of the above figures are based on the total weight of the thermosetting adhesive film.

[0082] The thermosetting adhesive film according to the present invention may further include at least one optional component as defined above.

[0083] The thermosetting adhesive film according to the present invention is self-supporting. The term "self-supporting adhesive film" means an adhesive film that maintains its integrity even without a substrate. In the context of the present invention, "liner" or "removable liner" is not considered a substrate.

[0084] The thermosetting adhesive film according to the present invention preferably has a total thickness in the range of 3 μm to 500 μm.

[0085] The thermosetting adhesive film according to the present invention preferably exhibits an extrusion strength of at least 3 MPa, and more preferably at least 3.5 MPa.

[0086] Unlike solvent-based adhesive compositions that require drying before crosslinking, the thermosetting adhesive film according to the present invention can be used immediately and can be rapidly crosslinked on or between multiple substrates. In the case of a thermosetting adhesive film according to the present invention with a thickness of 100 μm, the crosslinking time was observed to be approximately 10 minutes at 80°C.

[0087] Goods According to the fourth aspect, the following: First circuit board, Second substrate, and A thermosetting adhesive film according to the present invention, which is placed between the first substrate and the second substrate. Articles including the following will be provided.

[0088] In another embodiment, the article includes a first substrate, a second substrate, and a thermosetting adhesive film of the present invention positioned between the two substrates and in direct contact with the two substrates.

[0089] The first substrate and / or the second substrate may be a single material and a single layer, or may consist of multiple layers of the same or different materials. The layers may be continuous or discontinuous.

[0090] The base materials of the articles described herein may have a variety of properties, including rigidity (e.g., a hard base material, i.e., the base material cannot be bent with both hands or breaks when bent with both hands), flexibility (e.g., a flexible base material, i.e., the base material can be bent with less force than that of both hands), porosity, conductivity, lack of conductivity, and combinations thereof.

[0091] The base material of the article can take various forms, including, for example, fibers, threads, yarns, textiles, nonwovens, films (e.g., polymer films, metallized polymer films, continuous films, discontinuous films, and combinations thereof), foils (e.g., metallic foils), sheets (e.g., metallic sheets, polymer sheets, continuous sheets, discontinuous sheets, and combinations thereof), and combinations thereof.

[0092] In preferred embodiments, at least one of the substrates can be selected from metals, such as metal-fired paste, anodic aluminum, tin, molybdenum, silver, conductive metal oxides, such as indium tin oxide (ITO), fluorine-doped tin oxide, aluminum-doped zinc oxide, etc., glass, such as ink glass, bare glass, resins, such as polycarbonate, polybutylene terephthalate, and polyamide. More suitable metals include copper, gold, palladium, platinum, aluminum, indium, silver-plated copper, silver-plated aluminum, tin, and tin-plated copper. Preferably, both substrates are selected from one of the aforementioned materials.

[0093] According to another embodiment of this preferred embodiment, articles can be multilayered by laminating further substrates using the thermosetting adhesive film of the present invention.

[0094] For single-layer articles, the film thickness is preferably in the range of 3 μm to 500 μm. For multi-layer articles, the film thickness is preferably 10 μm to 1000 μm.

[0095] In one embodiment, an article having a first substrate and a second substrate is manufactured by bringing the first substrate into contact with one of the first main surfaces of a thermosetting adhesive film, bringing the second substrate into contact with the second main surface of the film so that the second main surface of the film is in direct contact with the second substrate, and curing the adhesive film by applying heat at a temperature of less than 100°C, preferably 60°C to 80°C, and applying arbitrary pressure to the article so that the two substrates are bonded together.

[0096] In another embodiment, an article having a first substrate and a second substrate is manufactured by contacting the first substrate with a first main surface of either one of the thermosetting adhesive films, and applying heat to the adhesive film at a temperature of 40°C to 60°C before or after applying the adhesive film to the first substrate to form a pre-laminate, which can be stored and transported to another location. During pre-lamination, partial aggregation may occur in the thermoplastic polymer (A), but the composition has not yet begun to cure or crosslink. When ready, the pre-laminate is used to form an article by contacting the second substrate with the second main surface of the film so that the second main surface of the film is in direct contact with the second substrate, and the final article is manufactured by curing the adhesive film by applying heat at a temperature of less than 100°C, preferably 60°C to 80°C, and applying any pressure (e.g., membrane or bladder press, heated platen) to the article so that the two substrates are bonded via the adhesive film.

[0097] The composition can be applied to a substrate using any suitable application method, including automatic fine wire dispensing, jet dispensing, slot die coating, roll coating, gravure coating, transfer coating, pattern coating, screen printing, spray coating, filament coating, extrusion, air knife, trailing blade, brushing, dipping, doctor blade, offset gravure coating, funnel gravure coating, and combinations thereof. The composition can be applied as a continuous or discontinuous coating, in single layers or multilayers, or in combinations thereof.

[0098] As is understood, the time and temperature curing profiles of each thermosetting adhesive film differ, and different compositions can be designed to provide curing profiles suitable for specific industrial manufacturing processes.

[0099] use A fifth aspect of the present invention provides the use of a composition according to the present invention, or a thermosetting adhesive film according to the present invention, or an article according to the present invention in the manufacture of automotive parts, truck bed covers, textile laminations, assemblies, and electronic equipment.

[0100] Thermosetting adhesive films are useful for a variety of applications, including, for example, temporarily bonding at least one substrate, permanently bonding at least one or two substrates, protecting substrates, restricting or preventing movement of a first substrate relative to a second substrate, and combinations thereof. Thermosetting adhesive films are also useful in a variety of processes, including, for example, manufacturing processes (e.g., bonding two parts of an article and maintaining the two parts in a fixed relationship with each other during the manufacturing process), shipping processes, stacking processes, and combinations thereof.

[0101] Thermosetting adhesive films can be used in the manufacture of a variety of items, including, for example, automotive parts, truck bed covers, textile laminations, various assemblies, and electronic equipment.

[0102] Examples of suitable electronic devices include, but are not limited to, wearable electronic devices (e.g., watches and glasses), handheld electronic devices (e.g., telephones (e.g., mobile phones and smartphones), cameras, tablets, e-readers, monitors (e.g., monitors used in hospitals by medical professionals, athletes, and individuals), clocks, calculators, mice, touchpads, and joysticks), computers (e.g., desktop and laptop computers), computer monitors, televisions, media players, or other electronic components. [Examples]

[0103] Examples The following examples are intended to help those skilled in the art to better understand and practice the present invention. The scope of the present invention is not limited by the examples but is defined by the appended claims. Unless otherwise specified, all parts and percentages are by weight.

[0104] raw materials: Vitel® 3300 is a thermoplastic polyester polymer with a weight molecular weight (Mw) of 63,000 g / mol and an optimal activation temperature of 125°C, and is available from Bostik.

[0105] KURARITY® LA4285 is a thermoplastic acrylic block copolymer with a weight molecular weight (Mw) of 40,000 g / mol and an optimal activation temperature of 140°C to 160°C, and is available from Kuraray.

[0106] HF4003LH-5 is a thermoplastic polyurethane polymer with a weight molecular weight (Mw) of 80,000 g / mol and an optimal activation temperature of 110°C to 130°C, and is available from Huafeng Chemical.

[0107] VYLON BX1001 is a thermoplastic polyester polymer with a weight molecular weight (Mw) of 28,000 g / mol and an optimal activation temperature of 82°C, and is available from TOYOBO.

[0108] Pearlstick (trademark) 45-60 / 08 is a thermoplastic polyurethane polymer with a weight molecular weight (Mw) of 60,000 g / mol and an optimal activation temperature of 40-70°C, and is available from Lubrizol.

[0109] WH6190A is a thermoplastic polyurethane polymer with a weight molecular weight (Mw) of 50,000 g / mol and an optimal activation temperature of 55°C, and is available from Wanhua Chemical.

[0110] P60 / 64 is a thermoplastic polyurethane polymer with a weight molecular weight (Mw) of 60,000 g / mol and an optimal activation temperature of 50°C, and is available from GUANGZHOU FTRT CHEMICAL CO., LTD.

[0111] CAPA® 6800 is a thermoplastic polyester polymer derived from polycaprolactone monomers, with a weight molecular weight (Mw) of 80,000 g / mol and an optimal activation temperature of 60°C, and is available from Perstorp.

[0112] KURARITY® LA2140 is a thermoplastic acrylic block copolymer with a weight molecular weight (Mw) of 40,000 g / mol and an optimal activation temperature of 40°C, and is available from Kuraray.

[0113] HYBRAR® 5125 is a styrene block copolymer with a weight molecular weight (Mw) greater than 10,000 g / mol and an optimal activation temperature of 80°C, and is available from Kuraray.

[0114] FZPE-A03130 is an amorphous polyester polyol with a weight molecular weight (Mw) of 3000 g / mol and is available from GUANGZHOU FTRT CHEMICAL CO., LTD.

[0115] Addolink (trademark) TT is TDI uretdione and is available from Rhein Chemie.

[0116] MEK is a methyl ethyl ketone, an organic solvent with a boiling point of 70°C to 80°C, and is available from Sinopharm.

[0117] Silquest A-189 is a silane available from Momentive.

[0118] Carbon black is a pigment available from Cabot.

[0119] BYK-141 is an antifoaming agent available from BYK.

[0120] BYK-3550 is a leveling agent available from BYK.

[0121] Preparation of compositions according to the present invention and thermosetting adhesive films obtained from said compositions (Examples 1 to 7) The compositions of Examples 1 to 7 according to the present invention were prepared using the components listed in Table 1 below. The content shown in Table 1 is expressed in grams (g).

[0122] Each thermosetting adhesive film obtained from the composition according to the present invention was manufactured according to the following steps: (1) The thermoplastic polymer (A), polyester polyol (B), and additives were added to the organic solvent (D) and slowly stirred at a temperature below 65°C for about 10 hours until the polymer dissolved; (2) Once dissolved, the solution was cooled to room temperature. Then the polyisocyanate (C) was introduced, the mixture was transferred to a suitable container, and rapidly stirred using a high-speed mixer at 2000 revolutions per minute (rev / min) for 1 minute twice; (3) The dispersion obtained in step (2) was poured onto the silicone-treated paper using a 500 μm film applicator. The adhesive film was left at room temperature for 1 hour while being suctioned, and the organic solvent (D) was evaporated.

[0123] Preparation of comparative compositions (CEx.1 to CEx.5) and their thermosetting adhesive films (CEx.1 to CEx.4) The compositions of Comparative Examples 1 to 5 were prepared using the ingredients listed in Table 1 below. The content shown in Table 1 is expressed in grams (g).

[0124] The thermosetting adhesive films obtained from CEx.1 to CEx.4 were manufactured using the procedure described above, in the same manner as in Examples 1 to 7 according to the present invention. Component (A) was replaced with the thermoplastic polymers Vitel® 3300, KURARITY® LA4285, and HF4003LH-5, respectively (CEx.2 to 4), or omitted (CEx.1).

[0125] CEx.5 corresponds to the composition of Example 2 according to the present invention, and although the weight of organic solvent (D) was 35% of the total weight of the composition, it was observed to form a gel rather than a homogeneous mixture, and therefore further testing was not possible.

[0126] Test method: Self-supporting: After evaporating the organic solvent (D), the self-supporting properties of the adhesive films obtained from the compositions of Examples 1-7 and Comparative Examples 1-4, prepared as described above, were tested by peeling them off the silicone-treated paper by hand. The observed results were recorded in Table 2 according to the following scale: A uniform film is formed and can be peeled off by hand. -〇 A uniform film cannot be formed (for example, dots are scattered and the surface is not uniform) - ×

[0127] Extrusion strength: Preparation of the adhesive film: Each of the compositions from the present invention and comparative examples obtained above was applied to one side of a removable liner. The organic solvent was then evaporated at room temperature for 1 hour to form an adhesive film; preferably, heating to 40°C to 70°C could accelerate the evaporation.

[0128] Sample pre-lamination: The adhesive films of the present invention example and comparative example were each cut to a size of 25 x 25 mm and pre-laminated on a heated platform using a test coupon. The test coupon consisted of an ink-coated glass block and a window-like component made separately from anodized aluminum. The adhesive film was uniformly applied to the surface of the ink-coated glass block on the platform at a temperature of 50°C, and the adhesive film was pressed for 30 seconds using a 500g weight to remove the liner from the adhesive film. The ink-coated glass block and window-like component were heated to 225 mm under a temperature of 60°C and a pressure of 2 kg. 2 The bonded area was then pressed for another 30 seconds. This pre-lamination process helps activate the fusion of the thermoplastic polymer with the initial bond.

[0129] Final lamination / thermosetting process: The specimens obtained above were transferred to a heat compressor and the final lamination / thermosetting process was performed at a temperature of 80°C. The heat compressor had flat metal thermos blocks at the top and bottom (both metal blocks were pre-set to 80°C). The final lamination was performed by crosslinking and curing the adhesive film while heating at 80°C for 10 minutes under a pressure of approximately 2 bar (typically 3-6 specimens were heated and pressurized at once). The samples were transferred from the heat compressor to room temperature and then continued to be compressed at a weight of 2 kilograms for 6 minutes.

[0130] Sample Test Extrusion strength tests were performed using a universal testing machine and punch in an environment of 23±2℃ and 50%±5% relative humidity. The punch applied compressive force to the metal block of the test coupon at a pressing speed of 2 mm / min until the assembly could no longer support the load. The maximum load was recorded in Table 2, and the extrusion strength was calculated by dividing the maximum load by the bonding area.

[0131] Adhesive films exhibiting an extrusion strength of at least 3 MPa, preferably at least 3.5 MPa, are considered acceptable.

[0132] [Table 1]

[0133] [Table 2]

[0134] As can be seen from Table 2, once peeled off, the adhesive films obtained from compositions Ex.1 to Ex.7 were all self-supporting and flexible enough to be rolled. In particular, it was noted that the compositions of Examples 1 to 7 had better mixing quality, higher film-forming properties, and made it possible to obtain thinner and more homogeneous films.

[0135] The composition of CEx.1 corresponds to Ex.1 to Ex.7 according to the present invention, which does not contain thermoplastic polymer (A), and it was observed that it could not form a homogeneous self-supporting film. Compared with adhesive films derived from CEx.2 to Ex.4, the adhesive films obtained from Ex.1 to Ex.7 showed superior extrusion strength after curing.

[0136] While several preferred embodiments have been described, many modifications and changes may be made in light of the above teachings. Therefore, it is understood that the present invention may be carried out in ways other than those specifically described, without departing from the scope of the appended claims.

Claims

1. below: (A) At least one thermoplastic polymer having a weight molecular weight (Mw) of 10,000 g / mol or more and an optimal activation temperature of 100°C or less. (B) At least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, (C) At least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, and (D) at least one organic solvent, which is present in an amount of more than 36% to 95% of the total weight of the composition. A composition containing the following:

2. The composition according to claim 1, wherein the optimal activation temperature of component (A) is less than 85°C, preferably 30°C to less than 80°C, more preferably 30°C to less than 70°C, and even more preferably 30°C to less than 60°C.

3. The composition according to claim 1 or 2, wherein component (A) is selected from the group consisting of thermoplastic polyurethane polymers, polyester polymers, acrylic polymers, ethylene-vinyl acetate copolymers, styrene block copolymers, polyvinyl acetol, styrene acrylonitrile, polyolefins, polyacrylonitrile, ethylene vinyl acetate terpolymers, functionalized ethylene vinyl acetate, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene butadiene copolymers and / or block copolymers, and is preferably selected from thermoplastic polyurethane polymers, polyester polymers, acrylic polymers, styrene block copolymers, and combinations thereof.

4. The composition according to any one of claims 1 to 3, wherein the component (B) is selected from amorphous polyester polyols, semicrystalline polyester polyols, crystalline polyester polyols, and combinations thereof, preferably amorphous polyester polyols, semicrystalline polyester polyols, and combinations thereof.

5. The composition according to any one of claims 1 to 4, wherein the NCO / OH molar ratio of the composition is in the range of 0.1 to 8.

6. The composition according to any one of claims 1 to 5, wherein component (D) is selected from the group consisting of ketones, preferably aliphatic ketones, more preferably acetone, methyl ethyl ketone (MEK), 2-pentanone, 3-pentane, methyl isobutyl ketone, ethyl acetate, and combinations thereof.

7. The composition according to any one of claims 1 to 6, further comprising at least one component selected from polyols, silanes, pigments, defoamers, leveling agents, stabilizers, dyes, and mixtures thereof, which is different from component (B).

8. Based on the total weight of the composition (A) At least one thermoplastic polymer in an amount of 1% to 95% by weight, preferably 10% to 40% by weight, having a weight molecular weight (Mw) of 10,000 g / mol or more, and an optimal activation temperature of 100°C or less, preferably less than 85°C, preferably between 30°C and less than 80°C, more preferably between 30°C and less than 70°C, and even more preferably between 30°C and less than 60°C. (B) At least one polyester polyol having a weight molecular weight (Mw) of less than 10,000 g / mol, in an amount of 0.01% to 80% by weight, preferably 5% to 40% by weight. (C) 0.05% to 20% by weight, preferably 0.5% to 5% by weight, of at least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, and (D) At least one organic solvent in an amount of more than 36% by weight to 95% by weight, preferably 50% to 85% by weight. A composition according to any one of claims 1 to 7, comprising:

9. The following steps: 1) A step of preparing a composition by dispersing component (C) in a mixture containing at least one component (A), at least one component (B), at least one component (D) and any component or additive as described in any of claims 1 to 8; A step of applying the composition obtained in any 1a) step 1) onto a peelable liner, 2) A step to remove component (D) from the composition obtained in step 1) or 1a). A method for preparing a thermosetting adhesive film, including [the specified element].

10. The method for preparing a thermosetting adhesive film according to claim 9, wherein the peelable liner in step 1a) has a non-adhesive surface to which the composition is applied.

11. A thermosetting adhesive film obtained by the method described in claim 9 or 10.

12. (A) At least one thermoplastic polymer in an amount of 1% to 95% by weight, preferably 30% to 90% by weight, having a molecular weight (Mw) of 10,000 g / mol or more, and an optimal activation temperature of 100°C or less, preferably less than 85°C, preferably between 30°C and less than 80°C, more preferably between 30°C and less than 70°C, and even more preferably between 30°C and less than 60°C. (B) At least one polyester polyol having a molecular weight (Mw) of less than 10,000 g / mol, in an amount of 0.01% to 80% by weight, preferably 10% to 50% by weight. (C) 0.1% to 20% by weight, preferably 1% to 10% by weight, of at least one polyisocyanate having at least two isocyanate groups and at least one uretdione group in one molecule, and (D) At least one organic solvent in an amount of less than 2.0% by weight, preferably less than 0.5% by weight, and more preferably less than 0.1% by weight (all of the above are based on the total weight of the thermosetting adhesive film) A thermosetting adhesive film containing [the specified element].

13. The thermosetting adhesive film according to claim 11 or 12, wherein the total thickness is in the range of 3 μm to 500 μm.

14. A thermosetting adhesive film according to claim 11 or 12, exhibiting an extrusion strength of at least 3 MPa, preferably at least 3.5 MPa.

15. First substrate, Second substrate, and A thermosetting adhesive film according to any one of claims 11 to 14, disposed between the first substrate and the second substrate. Articles containing.

16. Use of the composition according to any one of claims 1 to 8, or the thermosetting adhesive film according to any one of claims 11 to 14, or the article according to claim 15, in the manufacture of automotive parts, truck bed covers, textile laminations, assemblies, and electronic equipment.

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