Laminate containing adherend, primer and sealant, method for producing same, primer composition, and use of dicarbonyl compound

Abstract

To provide a laminate having an adherend, a sealant on the adherend, and a primer therebetween, in which the sealant can be separated from the adherend more easily than before. To provide a primer, sealant, adhesive, etc. that can be easily debonded. To enable debonding by heating. [Solution] A laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, wherein at least one of the sealant and the primer comprises a polyurethane and / or polyurea and a dicarbonyl compound. A primer composition comprising a polyurethane and / or polyurea and a dicarbonyl compound.

Description

[Technical Field]

[0001] The present disclosure relates to a laminate including an adherend, a primer, and a sealant, a method for producing the same, a primer composition, and use of a dicarbonyl compound. The present disclosure also relates to an assembly in which multiple adherends are bonded to each other via an adhesive and a primer. [Background technology]

[0002] Laminates having an adherend, a sealant on the adherend, and a primer therebetween are known for use in building materials, vehicle parts, and the like. Various laminates are formed by applying a sealant to the adherend (for example, the surface of a building material or vehicle part) via a primer. Also known are assemblies in which multiple adherends are bonded together with an adhesive, and the adhesive may adhere to the adherend via the primer.

[0003] Research is currently being conducted into methods for recovering valuable materials from waste.

[0004] Non-Patent Document 1 relates to a method for obtaining high-value chemicals and materials from post-consumer waste polymers. This document describes the use of urea bonds in polyurea, which are converted into vinylic amides by heat treatment with acetylacetone. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] Youwei Ma et al., Chemical Upcycling of Conventional Polyureas into Dynamic Covalent Poly(aminoketoenamide)s, Angew. Chem., 2023, 135, e202212870 Summary of the Invention [Problem to be solved by the invention]

[0006] Sealants or adhesives that have adhered to adherends are difficult to separate or remove, which can cause problems when they are reused or disposed of.

[0007] In this context, the present disclosure aims to provide a laminate having an adherend, a sealant on the adherend, and a primer therebetween, in which the sealant can be more easily separated from the adherend than in the past. Also, the present disclosure aims to provide a laminate in an assembly having multiple adherends bonded to one another via an adhesive and an associated primer, in which the adhesive can be more easily separated from the adherend than in the past.

[0008] The present disclosure also aims to provide methods for producing such laminates and assemblies, and to provide primer compositions that can be used in such laminates or assemblies.

[0009] Another object of the present disclosure is to provide a method for using a dicarbonyl compound in debonding a sealant, adhesive, and / or primer adhered to an adherend. In the present invention, "debonding" can mean weakening the adhesion between two components that are directly or indirectly adhered to each other, or even separating the components from each other. For example, "debonding" can mean weakening the adhesion between an adherend and a sealant or adhesive (and even a primer) in a laminate having an adherend and a sealant on the adherend and a primer therebetween, or in an assembly having multiple adherends bonded to each other via an adhesive and an associated primer, or even separating the adherends from each other.

[0010] Additionally, "heat-dependent debonding" can mean weakening the bond between, or even separating, two components that are directly or indirectly bonded to one another by heat treating the two components. [Means for solving the problem]

[0011] The problems of the present disclosure can be solved by the following aspects of the present invention: <Aspect 1> A laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, A laminate, wherein at least one of the sealant and the primer contains polyurethane and / or polyurea and a dicarbonyl compound. <Aspect 2> 2. The laminate of embodiment 1, wherein the sealant and the primer both comprise polyurethane and / or polyurea, and the primer comprises a dicarbonyl compound. <Aspect 3> 3. The laminate according to aspect 1 or 2, wherein the content of the dicarbonyl compound in the sealant and / or the primer is 0.1 to 80% by volume based on the total volume of the polyurethane and / or polyurea and the dicarbonyl compound. <Aspect 4> Aspect 4. The laminate according to any one of aspects 1 to 3, wherein the dicarbonyl compound includes at least one selected from 1,3-diketones, acetoacetic esters, and acetoacetic amides. <Aspect 5> A laminate according to any one of aspects 1 to 4, wherein the dicarbonyl compound includes at least one selected from acetylacetone and methylacetoacetate. <Aspect 6> Aspect 6. The laminate of any one of aspects 1 to 5, wherein the adherend is made of a material selected from the group consisting of plastic, ceramic, concrete, rubber, glass, metal, and mortar. <Aspect 7> 7. The laminate according to any one of aspects 1 to 6, wherein the adherend is a building material or a vehicle part. <Aspect 8> A primer composition comprising a polyurethane and / or polyurea and a dicarbonyl compound. <Aspect 9> 1. A method for manufacturing a laminate, comprising: the laminate has an adherend, a sealant on the adherend, and a primer between the adherend and the sealant; (a) providing an adherend; (b) applying a primer composition onto the adherend to form a primer layer; (c) applying a sealant composition over the primer layer; and (d) curing the applied sealant composition to form a sealant; Including, The method, wherein at least one of the sealant composition and the primer composition comprises a polyurethane and / or a polyurea and a dicarbonyl compound. The application of the sealant composition is preferably a coating of the sealant composition. <Aspect 10> Use of a dicarbonyl compound for heat-dependent debonding of a sealant or adhesive and / or primer containing polyurethane and / or polyurea and adhering to an adherend. <Aspect 11> An assembly having a first adherend, an adhesive, and a second adherend, the first adherend and the second adherend being joined together by the adhesive, An assembly, wherein at least one of the adhesive and a primer used in conjunction with the adhesive comprises at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine, and a dicarbonyl compound. <Aspect 12> 12. The assembly of claim 11, wherein the adhesive and the primer are substantially entirely surrounded by the first adherend and the second adherend. <Aspect 13> The assembly according to embodiment 11 or 12, further comprising at least one of the features described in embodiments 2 to 6 (where "sealant" is to be read as "adhesive"). [Effects of the Invention]

[0012] The present invention provides a laminate having an adherend, a sealant on the adherend, and a primer therebetween, which enables heat-dependent debonding. This makes it easier than ever to separate the sealant from the adherend. The present invention also provides an assembly having multiple (e.g., two) adherends bonded to each other via an adhesive and an associated primer, which enables heat-dependent debonding. This makes it easier than ever to separate the adhesive from the adherend. The present invention also provides methods for producing such laminates and assemblies, as well as primer compositions that can be used in such laminates or assemblies. The present invention also provides methods for using dicarbonyl compounds that can debond a sealant or adhesive and / or primer adhered to an adherend as needed. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic cross-sectional view of a laminate according to the present invention. [Figure 2] FIG. 2 is a photograph showing the results of the adhesion test according to Example 1 (first test: S1, second test: S2, third test: S3). [Figure 3] FIG. 3 is a photograph showing the results of the adhesion test according to Comparative Example 1 (first test: S1, second test: S2, third test: S3). DETAILED DESCRIPTION OF THE INVENTION

[0014] <<Laminate>> The laminate according to the present invention comprises: A laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, At least one of the sealant and the primer contains polyurethane and / or polyurea and a dicarbonyl compound.

[0015] As described above, various laminates are formed by applying a sealant via a primer to an adherend (for example, the surface of a vehicle or building material) (for example, by coating on vehicle components or by filling in building joints, etc.) In conventional laminates, it is not easy to remove the sealant from the adherend, which can cause problems when reusing or disposing of the laminate.

[0016] In response to this, the present inventors have discovered that by incorporating a dicarbonyl compound into a sealant and / or primer containing polyurethane and / or polyurea, it is possible to debond the sealant as needed in a heat-dependent manner (this is also referred to as "debonding-on-demand").

[0017] Specifically, by causing heat-dependent decomposition of polyurethane and / or polyurea by dicarbonyl compounds, the integrity of the sealant and / or primer and / or its adhesive strength to the substrate can be weakened, thereby making it easier to separate and remove (e.g., peel) the sealant (and further the primer) from the substrate.

[0018] According to the present invention, when it becomes necessary to remove the sealant (and even the primer) from building materials or vehicle windshields or body components, for example, during disposal, the sealant can be separated relatively easily by heat treatment.

[0019] Each component of the inventive aspects of the present disclosure will be described in more detail below.

[0020] <Dicarbonyl compounds> A dicarbonyl compound is a compound having two carbonyl groups (-C(=O)-) in the molecule. The dicarbonyl compound is preferably a 1,3-dicarbonyl compound. A 1,3-dicarbonyl compound has a structure in which two carbonyl groups are directly bonded to one carbon atom.

[0021] Examples of dicarbonyl compounds include 1,3-diketones, derivatives of 3-oxobutyric acid, acetoacetic esters, and acetoacetic amides. One dicarbonyl compound may be used alone, or two or more may be used in combination. Examples of dicarbonyl compounds also include β-keto acid esters and β-keto acid amides.

[0022] 1,3-diketones include acetylacetone and 2,4-hexadione.

[0023] Examples of 1,3-diketones include those in which both terminal substituents are alkyl groups with chains longer than methyl, or those in which the ring is condensed, such as a cyclohexane ring.

[0024] For example, 1,3-diketones include compounds having the following general formula (1):

[0025] [ka]

[0026] In formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, or may be joined together to form a cyclic structure.

[0027] In formula (1), R 1 and R 2 are each independently preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably methyl or ethyl.

[0028] In formula (1), R 1 and R 2 When these are taken together to form a cyclic structure, the cyclic structure may be, for example, a cycloalkylene ring (such as a cyclohexane ring) which may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms (such as a methyl group or an ethyl group).

[0029] Examples of acetoacetic acid esters include methyl acetoacetate (methyl acetoacetate) and ethyl acetoacetate (ethyl acetoacetate). Methyl acetoacetate has a relatively high boiling point, so it can be advantageously used to obtain a particularly stable debonding effect.

[0030] Furthermore, the acetoacetic acid ester includes a compound having the following general formula (2).

[0031] [ka]

[0032] In formula (2), R 3 and R 4 are each independently an alkyl group having 1 to 10 carbon atoms, or may be joined together to form a cyclic structure.

[0033] In formula (2), R 3 and R 4 are each independently preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably methyl or ethyl.

[0034] In formula (2), R 3 and R 4 When these are taken together to form a cyclic structure, the cyclic structure may be, for example, a cycloalkylene ring (such as a cyclohexane ring) which may have a substituent. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms (such as a methyl group or an ethyl group).

[0035] Examples of acetoacetamides include N,N-dimethylacetoacetamide and N,N-diethylacetoacetamide. Examples of acetoacetamides include those having a condensed carbon chain and those having a heterocycle containing a heteroatom other than the nitrogen atom (e.g., the oxygen atom in morpholine).

[0036] Furthermore, the acetoacetamide includes a compound having the following general formula (3).

[0037] [ka]

[0038] In formula (3), R 5 ~R 7 are each independently an alkyl group having 1 to 10 carbon atoms.

[0039] In formula (2), R 5 ~R 7 are each independently preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably methyl or ethyl.

[0040] In the laminate according to the present invention, at least one of the sealant and the primer contains a dicarbonyl compound. Preferably, the dicarbonyl compound is contained in both the sealant and the primer. In this case, better heat-dependent debonding is possible.

[0041] Preferably, the dicarbonyl compound is liquid at room temperature, which further improves the applicability of the sealant and / or primer containing the dicarbonyl compound, and makes it relatively easy to produce a laminate.

[0042] <Ingredient content> In one embodiment, the sealant, or primer, or sealant and primer, contains a dicarbonyl compound in an amount of 0.1 to 80% by volume, based on the total amount of polyurethane and / or polyurea and dicarbonyl compound. This dicarbonyl compound content may be 0.5% by volume or more, 1% by volume or more, 2% by volume or more, 5% by volume or more, 10% by volume or more, 12% by volume or more, 15% by volume or more, 20% by volume or more, 25% by volume or more, 30% by volume or more, or 35% by volume or more, and / or 90% by volume or less, 85% by volume or less, 80% by volume or less, 75% by volume or less, 70% by volume or less, 65% by volume or less, 60% by volume or less, or 55% by volume or less. This dicarbonyl compound content is preferably 1 to 75% by volume, more preferably 5 to 70% by volume, and even more preferably 10 to 65% by volume.

[0043] By ensuring that the amount of dicarbonyl compound in the sealant and / or primer is within the above range, it is possible to ensure a sufficient amount of components (particularly polymer components) necessary for the functions of the sealant and / or primer (e.g., adhesion, waterproofing, sealing properties), thereby ensuring sufficient performance of the sealant and / or primer. Furthermore, by ensuring that the amount of dicarbonyl compound in the sealant and / or primer is within the above range, it is possible to ensure a sufficient amount of dicarbonyl compound, thereby achieving a sufficient debonding effect.

[0044] <Polyurethane and / or polyurea> At least one of the sealant and the primer contains polyurethane and / or polyurea, which can impart desired functions (sealing properties, waterproofing properties, adhesive properties, etc.) to the sealant and the primer.

[0045] Polyurethanes and / or polyureas can be obtained by polymerization reactions of polyisocyanates with polyols and / or polyamines and contain, for example, urethane and / or urea groups.

[0046] Preferably, both the sealant and the primer contain polyurethane and / or polyurea, which improves the compatibility between the sealant and the primer, further increasing the adhesion between them.

[0047] Polyurethanes can be obtained by the polymerization reaction of polyisocyanates and polyols. Polyureas can be obtained by the polymerization reaction of polyisocyanates and polyamines. These polymers can be used alone or in combination.

[0048] (Polyisocyanate) "Polyisocyanate" means a compound having two or more isocyanate groups.

[0049] Polyisocyanates include diisocyanates, including aromatic, aliphatic, or cycloaliphatic diisocyanates with a molecular weight of less than 500 g / mol.

[0050] Specific polyisocyanate compounds are all isomers of toluene diisocyanate (TDI) (either in isomerically pure form or as a mixture of several isomers), naphthalene-1,5-diisocyanate (NDI), naphthalene-1,4-diisocyanate (NDI), diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,4'-diisocyanate and mixtures of 4,4'-diphenylmethane diisocyanate with the 2,4'-isomer, xylylene diisocyanate (XDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane diisocyanates, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate. Examples of suitable cycloaliphatic diisocyanates are the hydrogenated products of the above-mentioned aromatic diisocyanates, such as 4,4'-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), 1-methyl-2,4-diisocyanato-cyclohexane, hydrogenated p-tetramethylxylene diisocyanate (m-TMXDI, p-TMXDI). Further suitable diisocyanates are 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI) and dimer fatty acid diisocyanates. Examples of aliphatic diisocyanates include tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, lysine diisocyanate, and 1,12-dodecane diisocyanate (C12DI), which may be used alone or in combination.

[0051] (Polyol compound) The polyol compound is a compound having two or more OH groups in the molecule. Examples of the polyol compound include polyether polyols and polyester polyols, specifically, difunctional and / or trifunctional polypropylene glycols or polyethylene glycols, linear difunctional polyethylene glycol monomethyl ethers, random and / or block copolymers of ethylene oxide and propylene oxide, and polytetramethylene glycols (poly(oxytetramethylene) glycol, polyTHF) produced by acid polymerization of tetrahydrofuran.

[0052] More specific examples of polyols include polyesters made by condensation of dicarboxylic acids or tricarboxylic acids such as adipic acid, sebacic acid, glutaric acid, azelaic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimeric fatty acids, or mixtures thereof, with low molecular weight diols or triols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimeric fatty alcohols, glycerol, trimethylolpropane, or mixtures thereof.

[0053] Polyamines include aliphatic, alicyclic, or arylaliphatic primary diamines, aliphatic, alicyclic, or arylaliphatic primary triamines, ether group-containing aliphatic primary diamines, primary polyoxyalkylene triamines that are products from the amination of polyoxyalkylene triols, polyamines having two primary aliphatic amino groups and a tertiary amino group, polyamines containing three primary aliphatic amino groups and a tertiary amino group, polyamines containing two primary aliphatic amino groups and a secondary amino group, polyamines having primary and secondary amino groups, aromatic polyamines, and polyamidoamines.

[0054] Specific examples of polyamines include 1,3-pentanediamine (DAMP), 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,12-dodecanediamine, 1,3-diaminocyclohexane, bis-(4-aminocyclohexyl)methane (H12-MDA), bis-(4-amino-3-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-bis-(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene, These include benzene (MXDA), bis-hexamethylenetriamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) and higher homologues of linear polyethyleneamines such as polyethylenepolyamines having 5 to 7 ethyleneamine units (HEPA), dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), polyoxyalkylenediamines and polyoxyalkylenetriamines having molecular weights in the range of 200 to 500 g / mol.

[0055] <Laminate> The laminate has an adherend, a sealant on the adherend, and a primer between the adherend and the sealant. The adherend, primer, and sealant may be laminated one on top of the other in that order. They may be adhered to each other in the laminate.

[0056] Figure 1 is a schematic diagram of a laminate according to the present invention. The drawing is an exemplary illustration for explaining the present invention and is not drawn to scale. The laminate 10 in Figure 1 has a structure in which an adherend 11, a primer 12, and a sealant 13 are laminated in this order.

[0057] Such a laminate 10 can be produced, for example, by applying a primer composition to the surface of an adherend 11 and appropriately drying it to form a primer 12, and then applying a sealant composition onto the applied primer 12 and curing it to form a sealant 13. In the laminate 10, the adherend 11 and the sealant 13 are bonded to each other via the primer 12.

[0058] <Adherend> The substrate may have a surface for placement of the primer and sealant.

[0059] The shape of the adherend is not particularly limited, but may be, for example, a plate shape.

[0060] The adherend may be made of a material selected from the group consisting of plastic, ceramic, concrete, rubber, glass, metal and mortar. Preferably, the adherend is made of a material selected from the group consisting of plastic, glass and metal.

[0061] Examples of plastics include polyolefin resins (e.g., polyethylene, polypropylene, polybutylene), polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate), nylon resins, polymethyl methacrylate resins, polycarbonate resins, polystyrene resins, acrylonitrile-styrene copolymer resins, polyvinyl chloride resins, acetate resins, acrylonitrile-butadiene styrene resins, polyphenylene sulfide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyketone resins, polyetherketone resins, polyetheretherketone resins, polyimide resins, polyamide resins, and fluororesins. The glass may be soda-lime glass, quartz glass, borosilicate glass, or aluminosilicate glass.

[0062] Examples of metals include iron and aluminum. In particular, the adherend may be a metal plate or a coated steel plate, or may be a stainless steel plate, an ED plate obtained by electro-deposition coating (ED) on a stainless steel plate, or an aluminum plate.

[0063] The adherend may be a building material or a vehicle part. More specifically, the adherend may include wall materials, gypsum boards, sashes, and flooring materials, or vehicle parts (e.g., interior and exterior parts) and window materials. Vehicle parts may include bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, and rocker moldings. Vehicle window materials may include windshields.

[0064] <Sealant> The sealant may be a material that can impart properties such as sealing, waterproofing, and adhesiveness to an adherend. The sealant may have, for example, a layer or film shape. The sealant may have a thickness of 0.1 mm to 50 mm.

[0065] The sealant contains at least a polymer. In one embodiment, the sealant contains polyurethane and / or polyurea. For the polymer, reference can be made to the above description.

[0066] The sealant may be, for example, a member obtained by curing a sealant composition containing polyurethane and / or polyurea.

[0067] Preferably, the sealant comprises a moisture-curing polyurethane.

[0068] In one embodiment, the sealant contains a polyurethane and / or polyurea and a dicarbonyl compound. For details about the polyurethane and / or polyurea and the dicarbonyl compound, see the above description. In this case, the integrity and / or adhesiveness of the sealant is reduced in a heat-dependent manner, allowing for debonding as needed, making it relatively easy to separate and remove the sealant from the adherend.

[0069] The sealant may contain a solvent. The solvent may volatilize and disappear during the manufacturing process of the laminate, but may remain in the finished laminate. The solvent may be a known solvent, such as ethyl acetate or butyl acetate.

[0070] When containing a dicarbonyl compound, the sealant may have, for example, the following composition: - 0 to 80% by volume, 0 to 50% by volume, or even 10 to 50% by volume of polyurethane and / or polyurea - 0.1 to 80% by volume of dicarbonyl compounds - 0 to 30% by volume, or even 0 to 15% by volume of solvent

[0071] The sealant may further contain additives as needed, provided that the objects and effects of the present invention are not impaired. Examples of additives include fillers, pigments, antiblocking agents, dispersion stabilizers, thixotropic agents, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, antioxidants, UV absorbers, plasticizers, lubricants, antistatic agents, reinforcing materials, flame retardants, catalysts, antifoaming agents, thickeners, dispersants, and organic solvents.

[0072] <Primer> The primer may be a component that has the function of improving the adhesion between the adherend and the sealant. The primer may have, for example, a layer or film shape. The primer may have a thickness of 1 μm to 500 μm.

[0073] The primer may contain similar ingredients to the sealant, for example, the same types of polyurethanes and / or polyureas as the sealant.

[0074] The primer may be a layer-like member obtained by applying (particularly painting) a primer composition onto an adherend.

[0075] In one embodiment, the primer comprises polyurethane and / or polyurea, details of which polymers can be found above.

[0076] In a preferred embodiment, the primer contains polyurethane and / or polyurea and further contains a dicarbonyl compound. For details of the polyurethane and / or polyurea and dicarbonyl compound, please refer to the above description. In this case, the polyurethane and / or polyurea contained in the primer decomposes through heat treatment, thereby weakening the primer's integrity and / or adhesive strength to the substrate, thereby enabling debonding as needed through heat treatment. Therefore, according to this embodiment, residual sealant and / or primer on the substrate is avoided or reduced, and even if any remains, they can be removed relatively easily, allowing the sealant and even the primer to be peeled relatively cleanly from the substrate. The resulting adherend has a relatively clean surface after treatment, making it possible to reuse it, etc.

[0077] When containing a dicarbonyl compound, the primer may have, for example, the following composition: - 1 to 80% by volume, or even 1 to 20% by volume, of polyurethane and / or polyurea - 0.1 to 80% by volume of dicarbonyl compounds 0-95% by volume, 0-50% by volume, or even 0-5% by volume of solvent

[0078] If it does not contain a dicarbonyl compound, the primer may have, for example, the following composition: - 1 to 99% by volume, or 50 to 99% by volume of polyurethane and / or polyurea - 0-5% by volume or 0-1% by volume of solvent

[0079] The primer may contain a solvent. The solvent may volatilize and disappear during the manufacturing process of the laminate, but may remain in the finished laminate. Examples of the solvent include ethyl acetate, butyl acetate, and toluene. Of these, ethyl acetate and butyl acetate are preferred.

[0080] The primer may further contain additives as needed, provided that the objects and effects of the present invention are not impaired. Examples of additives include fillers, pigments, antiblocking agents, dispersion stabilizers, thixotropic agents, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, antioxidants, UV absorbers, plasticizers, lubricants, antistatic agents, reinforcing materials, flame retardants, catalysts, defoamers, thickeners, dispersants, and organic solvents.

[0081] <<Laminate manufacturing method>> The method for producing the laminate according to the present invention is not particularly limited, and the laminate according to the present invention can be produced, for example, by the following production method according to the present invention.

[0082] 1. A method for making a laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, comprising: (a) providing an adherend (providing step); (b) applying a primer composition onto an adherend to form a primer layer (primer application step); (c) applying a sealant composition onto the primer layer (sealant application step); and (d) curing the applied sealant composition to form a sealant (curing step); Including, At least one of the sealant composition and the primer composition contains polyurethane and / or polyurea and a dicarbonyl compound. method.

[0083] For details of the method for producing the laminate according to the present invention (for example, each component such as adherend, sealant, primer, dicarbonyl compound, etc.), reference can be made to the above description of the laminate according to the present invention.

[0084] (Providing process) In the providing step, an adherend is provided. The surface of the laminate may be cleaned in advance. Cleaning can be performed, for example, by wiping with an alcohol-impregnated wipe.

[0085] (Primer application process) In the primer application step, a primer composition is applied onto an adherend to form a primer layer. "Application" may be performed by, for example, "painting."

[0086] Examples of application methods include a brush, roller, spray, and rod. More specific application methods include a dip coating method, a double roll coater, a slit coater, an air knife coater, a wire bar coater, a slide hopper, spray coating, a blade coater, a doctor coater, a squeeze coater, a reverse roll coater, a transfer roll coater, an extrusion coater, a curtain coater, a dip coater, a die coater, a coating method using a gravure roll, a screen printing method, a dip coating method, a spray application method, a spin coating method, and an inkjet method.

[0087] The applied primer composition may be optionally dried. Drying may be performed by leaving the composition to stand or by air drying at room temperature or at 15°C to 35°C for 1 minute to 5 hours. For example, by drying the applied primer composition, at least a portion of the solvent in the primer composition can be evaporated to form a film-like primer.

[0088] (Primer composition)

[0089] The primer composition contains at least polyurethane and / or polyurea. Preferably, the primer composition may be the primer composition of the present invention, i.e., contains polyurethane and / or polyurea and a dicarbonyl compound. For details of polyurethane, polyurea, polyisocyanate, polyol, polyamine, dicarbonyl compound, etc., please refer to the above descriptions.

[0090] The primer composition may further contain a solvent, such as ethyl acetate, butyl acetate, or toluene. Of these, ethyl acetate and butyl acetate are preferred.

[0091] Although the use of a solvent is useful for forming a thin, uniform layer, from the viewpoint of further enhancing the debonding effect of the dicarbonyl compound while ensuring the amount of polymer in the primer composition, it is preferable to keep the amount of solvent in the primer composition as small as possible. It is also possible to replace at least a portion of the solvent with a dicarbonyl compound that is liquid at room temperature. In such a case, the content of the polymer (and further the dicarbonyl compound) increases, so that the desired functions (e.g., sealing properties, waterproofing properties, adhesion properties, etc.) of the primer composition can be more effectively obtained, and a better debonding effect can be achieved.

[0092] The primer composition may, for example, have the following composition: - 1 to 80% by volume or even 1 to 20% by volume of polyurethane and / or polyurea - 0.1 to 80% by volume of dicarbonyl compounds 0-95% by volume, 0-50% by volume, or even 0-5% by volume of solvent

[0093] The primer composition of the present invention may further contain additives as needed, provided that the object and effect of the present invention are not impaired. Examples of additives include fillers, pigments, antiblocking agents, dispersion stabilizers, thixotropic agents, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, antioxidants, UV absorbers, plasticizers, lubricants, antistatic agents, reinforcing materials, flame retardants, catalysts, defoamers, thickeners, dispersants, and organic solvents. The primer composition may contain, for example, activated carbon.

[0094] (Sealant application process) In the sealant application step, a sealant composition is applied on top of the primer. "Application" may be performed, for example, by "spreading" or by "filling" gaps between components, such as filling joints in construction. Application methods include the same methods as those described above for the primer application step (e.g., using a brush, roller, spray, rod, etc.).

[0095] The sealant composition contains at least polyurethane and / or polyurea. For details of polyurethane, polyurea, polyisocyanate, polyol, polyamine, dicarbonyl compound, etc., please refer to the above descriptions.

[0096] When containing a dicarbonyl compound, the sealant composition may have, for example, the following composition: - 0 to 80% by volume, 0 to 50% by volume, or even 10 to 50% by volume of polyurethane and / or polyurea - 0.1 to 80% by volume of dicarbonyl compounds - 0 to 30% by volume, or even 0 to 15% by volume of solvent

[0097] (hardening process) In the curing step, the applied sealant composition is cured to form a sealant. The curing treatment can be carried out according to a known method depending on the components contained in the sealant composition.

[0098] In one embodiment, the sealant contains a moisture-curable polyurethane. In this case, the sealant composition can be cured by contacting it with water (e.g., moisture in the air). Such moisture curing can be carried out, for example, by leaving it to stand under conditions of 15°C to 30°C and 30 to 60% relative humidity for 1 hour to 30 days (or even 1 to 10 days).

[0099] (Additional process) The method for producing a laminate according to the present invention may include an additional step. For example, an additional member may be placed on the sealant of the laminate formed through the above steps (a) to (d). The additional member is not particularly limited and may be made of the same material as described above for the adherend.

[0100] <<Using adhesive>> As described above, the effects of the present invention can also be achieved in an embodiment in which an "adhesive" is used instead of a "sealant." The "adhesive" may have the same composition and preferred ranges of each component as the above-mentioned "sealant." An assembly invention using an adhesive will be described below.

[0101] <Assembly> The present invention includes the following assembly invention: An assembly having a first adherend, an adhesive, and a second adherend, the first adherend and the second adherend being joined together by the adhesive, An assembly, wherein at least one of an adhesive and a primer used in conjunction with the adhesive contains polyurethane and / or polyurea and a dicarbonyl compound.

[0102] For details and preferred ranges of each component of this embodiment (for example, adherend, primer, polyurethane, polyurea, dicarbonyl compound, etc.), reference can be made to the above descriptions of the laminate according to the present invention and the method for producing the same.

[0103] The assembly according to the present invention can include a first adherend, an adhesive, and a second adherend. For example, the assembly can be formed by joining the first adherend and the second adherend together with the adhesive.

[0104] (glue) The adhesive may have the same composition and suitable ranges of each component as the above-mentioned "sealant." The adhesive is not particularly limited as long as it can bond a first adherend and a second adherend to each other.

[0105] In the assembly according to the present invention, at least one of the adhesive and the primer used in conjunction with the adhesive contains a polyurethane and / or a polyurea and a dicarbonyl compound. In one preferred embodiment, both the adhesive and the primer contain a polyurethane and / or a polyurea, and at least the primer contains a dicarbonyl compound.

[0106] In one embodiment, the adhesive and primer are substantially entirely surrounded by the first and second adherends, which substantially isolates the adhesive and primer from the external environment, thereby suppressing volatilization of the components and thereby maintaining the debonding effect for a long period of time.

[0107] "Enclosed on substantially all sides" can mean, for example, that the adhesive and primer are sandwiched and substantially sealed between one major surface of a first adherend and one major surface of a second adherend, thereby being substantially isolated from the external environment.

[0108] The method for producing the assembly according to the present invention is not particularly limited, but it can be produced, for example, by the following method: A method for producing an assembly having a first adherend, an adhesive, and a second adherend, the first adherend and the second adherend being bonded together by the adhesive, comprising: (a) providing a first adherend; (b) applying a primer composition onto a first adherend to form a primer layer; (c) applying an adhesive over the primer layer; (d) placing a second adherend over the applied adhesive; and (e) curing the applied adhesive; Including, At least one of the adhesive and the primer composition contains polyurethane and / or polyurea and a dicarbonyl compound; method.

[0109] For details and preferred ranges of each component of this manufacturing method of the assembly according to the present invention, reference can be made to the above description of the laminate according to the present invention and the manufacturing method thereof.

[0110] <<Debonding method>> The present invention also includes a debonding method, which may mean a method for weakening the bond between two members that are directly or indirectly bonded to each other, or even separating the two members from each other.

[0111] One embodiment of the debonding method of the present invention is a method for heat-dependent debonding of a sealant (and also a primer) from an adherend in a laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, or an assembly having two adherends bonded together via an adhesive and an associated primer, comprising: Heating the laminate at a temperature of 100°C to 160°C for 1 minute to 5 hours; Including, The primer comprises a polyurethane and / or polyurea and a dicarbonyl compound.

[0112] For details of the debonding method according to the present invention (for example, each component such as adherend, sealant, primer, dicarbonyl compound, etc.), reference can be made to the above descriptions of the laminate and assembly according to the present invention.

[0113] The debonding method of the present invention makes it possible to heat-dependently debond the sealant or adhesive (and also the primer) as needed in a laminate having an adherend, a sealant, and a primer disposed therebetween, or in an assembly having two adherends joined together via an adhesive and an associated primer. Specifically, by heat-dependently causing decomposition of the polymer by a dicarbonyl compound contained in the primer, the integrity of the primer and / or its adhesive strength to the adherend can be weakened, thereby making it easier to remove (separate, peel, etc.) the sealant or adhesive (and also the primer) from the adherend.

[0114] The heat treatment of the laminate may be carried out by a known method, for example, using a heating furnace, or by using an electric heater (such as a hot plate) to heat the back surface of the adherend by contacting it with the adherend. The heat treatment temperature is 100 to 160°C, or may be 110 to 150°C, or even 120 to 150°C. The heat treatment time is 10 seconds to 1 hour, or may be 20 seconds to 45 minutes, 30 seconds to 30 minutes, or 1 minute to 20 minutes.

[0115] <<How to use>> The present invention also includes a method of using a dicarbonyl compound. One embodiment of the method of use is the use of a dicarbonyl compound for heat-dependent debonding of a sealant or adhesive and / or primer that contains polyurethane and / or polyurea and is adhered to an adherend.

[0116] For details of this method of use according to the present invention (for example, constituent elements such as adherend, sealant, primer, dicarbonyl compound, etc.), reference can be made to the above descriptions of the laminate and assembly according to the present invention.

[0117] As described above, in a laminate having an adherend and a sealant with a primer disposed therebetween, or in an assembly having two adherends bonded to each other via an adhesive and an associated primer, if the laminate contains polyurethane and / or polyurea, the use of a dicarbonyl compound makes it possible to debond the sealant or adhesive (and even the primer) in a heat-dependent manner as needed.

[0118] In one embodiment of the method of use according to the present invention, a primer is disposed between an adherend and a sealant or adhesive, the sealant or adhesive containing a polyurethane and / or a polyurea, and the primer containing a polyurethane and / or a polyurea and a dicarbonyl compound. It is believed that the components of the sealant or adhesive and the primer are at least partially intermixed at the interface between the sealant or adhesive and the primer. Therefore, according to this embodiment, the polyurethane and / or a polyurea contained in the sealant or adhesive is thermally decomposed by the dicarbonyl compound in the primer at the interface between the sealant or adhesive and the primer, thereby weakening the adhesive strength of the sealant or adhesive. Furthermore, it is believed that the thermal decomposition of the polyurethane and / or a polyurea contained in the primer weakens the integrity of the primer itself and / or its adhesive strength to the adherend, thereby further weakening the adhesion of the sealant or adhesive to the adherend.

[0119] Therefore, according to this embodiment, the residue of the sealant or adhesive and / or primer on the adherend is avoided or reduced, and even if any remains, they can be removed relatively easily, so that the sealant or adhesive and even the primer can be peeled relatively cleanly from the adherend. The "adherend" obtained in this way has a relatively clean surface after treatment, making it possible to reuse it.

[0120] <<Application>> The laminate, the method for producing the laminate, the primer composition, and the method for use according to the present invention can be used, for example, in building materials and vehicle parts (for example, automobile parts).

[0121] The debonding method according to the present invention can also be used, for example, in the dismantling of buildings and vehicles (such as automobile parts) and the recovery of recyclable materials. [Example]

[0122] <<Example 1 and Comparative Examples 1 to 3>> A laminate was produced in which a sealant was adhered via a primer onto a glass substrate as an adherend, and the "on-demand debonding" was evaluated.

[0123] Example 1 (Manufacturing of laminates) The surface of a glass substrate (adherend) was wiped with a dustless wipe and 2-propanol and allowed to stand for 60 minutes. A primer composition containing "Hamatite MS-90" ("GP") and acetylacetone ("ACAC") as a dicarbonyl compound in a 50:50 volume ratio was then applied to the surface of the glass substrate using a No. 28 rod coater. The mixture was allowed to stand at room temperature for 60 minutes without ventilation, forming a primer on the glass substrate. A sealant composition (MDI / IPDI-based high-viscosity polyurethane one-component polyurethane (PU)) was then applied in three linear (bead) shapes using a 10 mm nozzle onto the formed primer. The sealant was then cured at 23°C and 50% relative humidity for 7 days to form a sealant, yielding a laminate according to Example 1.

[0124] The composition of Hamatite MS-90 ("GP") was as follows: - Polyurethane 25% by volume - Ethyl acetate 70% by volume - Activated carbon 5% by volume

[0125] (Adhesion evaluation) Adhesion Test (First Test S1): The first adhesion test was conducted on the laminate of Example 1 at 23°C and 50% relative humidity. Specifically, the adherend was fixed to a laboratory bench with a vice or clamp, and a slit was made with a blade at one end of the bead-shaped sealant to facilitate peeling. The cut end was held and a pulling force was applied at a 135° angle with pliers to promote peeling, peeling the sealant from the adherend surface. The peeling rate was approximately 10 cm / min. If peeling did not occur, a blade was applied to the stretched portion to induce fracture (tear) of the sealant. After peeling, the adherend's surface was observed, and the peeled area, the broken sealant area, and the broken primer area were compared and evaluated. The results are shown in Table 1.

[0126] Adhesion test (second time S2): After the first adhesion test, the laminate was left standing at 140°C for 4 hours, and then the sealant was peeled off from the adherend at a 135° angle in the same manner as above under conditions of 23°C and 50% relative humidity, and the adherend surface after peeling was observed. The results are shown in Table 1.

[0127] Adhesion test (third time S3): After the second adhesion test, the laminate was left to stand at 23°C for 1 hour, and then, in a ventilated environment, the sealant was peeled off from the adherend in a 135° direction in the same manner as above, and the surface of the adherend after peeling was observed.

[0128] The evaluation of the adhesion test was carried out according to the following criteria. "Sealant remaining": A portion of the primer and sealant remained on the adherend (cohesive failure "CF" occurred). "Primer remaining": The primer remained on the adherend, and no foam-like failure was observed (interfacial failure "AF" occurred). "Primer breakdown": The primer remained on the adherend, and foam-like breakdown of the primer was observed (primer breakdown "PB" occurred).

[0129] The components and evaluation results are shown in Table 1 and Figure 2. Figure 2 is a photograph showing the results of the adhesion test according to Example 1 (first test: S1, second test: S2, third test: S3).

[0130] <Comparative Example 1> A laminate was produced and evaluated in the same manner as in Example 1, except that the volume ratio of GP:ACAC in the primer was 100:0 (no ACAC was included). The results are shown in Table 1 and Figure 2. Figure 3 is a photograph showing the results of the adhesion test (first test: S1, second test: S2, third test: S3) for Comparative Example 1.

[0131] <Comparative Example 2> Except for the fact that the volume ratio of GP:ACAC in the primer was 0:100 (GP was not included), a laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0132] <Comparative Example 3> Except for the fact that the sealant was applied directly onto the adherend without using a primer, a laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0133] [Table 1]

[0134] The "Adhesion" item in Table 1 is an evaluation item related to the performance of the primer, and is marked "Good" if the adhesion of the sealant is improved compared to when no primer is used (Comparative Example 3), and marked "Poor" if the adhesion is not improved (the same applies to Tables 2 and 3).

[0135] As seen in Table 1 and Figures 2 and 3, in the laminate of Example 1, in which the primer contained a dicarbonyl compound (acetylacetone, ACAC), the primer remained on the adherend without any damage in the first peel test at room temperature (S1 in Figure 1). However, when peeled after heat treatment at 140°C (S2) and after a cooling period (S3), "primer damage," in which a portion of the primer deformed into bubbles, was observed (S2 and S3 in Figure 2). This indicates that heat-dependent debonding occurred. This phenomenon was not observed in the comparative example (S1 to S3 in Table 1 and Figure 3).

[0136] <<Example 2 and Comparative Examples 4 and 5>> Except for using methyl acetoacetate (MAA) instead of acetylacetone (ACAC), laminates according to Example 2 and Comparative Examples 4 and 5 were produced and evaluated using the component amounts shown in Table 2 in the same manner as in Example 1. The results are shown in Table 2 below.

[0137] [Table 2]

[0138] As can be seen in Table 2, heat-dependent "primer destruction" was also confirmed when methyl acetoacetate (MAA) was used instead of acetylacetone as the dicarbonyl compound.

[0139] <<Examples 3 to 4 and Comparative Examples 7 to 9>> Laminates of Examples 3 and 4 and Comparative Examples 7 to 9 were produced and evaluated in the same manner as in Example 1, except that the volume ratio of GP to ACAC in the primer was changed as shown in Table 3 below. The results are shown in Table 3. In Table 3, the second exposure to 140°C was a trigger for initiating heat-dependent debonding. In Table 3, the third exposure to room temperature after cooling was performed to confirm that the sealing layer was not simply melted or loosened by heating and peeled off.

[0140] [Table 3]

[0141] As can be seen in Table 3, heat-dependent "primer destruction" was observed even when the content of acetylacetone as a dicarbonyl compound was changed.

Claims

1. A laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, a laminate, wherein at least one of the sealant and the primer contains a polyurethane and / or a polyurea and a dicarbonyl compound, and the content of the dicarbonyl compound is 12% by volume or more and 90% by volume or less based on the total amount of the polyurethane, polyurea, and the dicarbonyl compound.

2. A primer composition comprising a polyurethane and / or polyurea and a dicarbonyl compound, wherein the content of the dicarbonyl compound is 12% by volume or more and 90% by volume or less based on the total of the polyurethane and polyurea and the dicarbonyl compound.

3. 1. A method for manufacturing a laminate, comprising: the laminate has an adherend, a sealant on the adherend, and a primer between the adherend and the sealant; (a) providing an adherend; (b) applying a primer composition onto the adherend to form a primer layer; (c) applying a sealant composition over the primer layer; and (d) curing the applied sealant composition to form a sealant; Including, At least one of the sealant composition and the primer composition contains a polyurethane and / or a polyurea and a dicarbonyl compound, and the content of the dicarbonyl compound is 12% by volume or more and 90% by volume or less based on the total amount of the polyurethane and polyurea and the dicarbonyl compound.

4. An assembly having a first adherend, an adhesive, and a second adherend, the first adherend and the second adherend being joined together by the adhesive, At least one of the adhesive and the primer used in conjunction with the adhesive contains polyurethane and / or polyurea and a dicarbonyl compound, and the content of the dicarbonyl compound is 12% by volume or more and 90% by volume or less based on the total of the polyurethane, polyurea, and dicarbonyl compound.

5. A method for heat-dependently debonding the sealant or adhesive from an adherend in a laminate having an adherend, a sealant on the adherend, and a primer between the adherend and the sealant, wherein at least one of the sealant and the primer comprises polyurethane and / or polyurea and a dicarbonyl compound, or in an assembly having a first adherend, an adhesive, and a second adherend, the first adherend and the second adherend being joined by the adhesive, wherein at least one of the adhesive and the primer used in conjunction with the adhesive comprises polyurethane and / or polyurea and a dicarbonyl compound, comprising: heating the laminate or assembly at a temperature of 100°C to 160°C; method.

6. Use of a dicarbonyl compound for heat-dependent debonding of a sealant or adhesive and / or primer containing polyurethane and / or polyurea and adhered to an adherend, the use comprising heating the sealant or adhesive and / or primer containing the dicarbonyl compound at a temperature of 100°C to 160°C.

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