Laminate

Abstract

The present invention provides a laminate that has an easily-decomposable coating layer while having characteristics of a siloxane structure such as slidability, peelability, antifouling properties, chemical resistance, heat resistance, cold resistance, flexibility, and electrically insulating properties. The present invention relates to a laminate comprising a base material and a coating layer that is formed on the base material, wherein the coating layer comprises a cross-linked substance that includes a siloxane structure which can be decomposed by an oxidizing agent.

Description

Laminate

[0001] The present invention relates to a laminate.

[0002] Silicone resins have properties such as flame retardancy, thermal stability, and chemical stability, and are used in a wide range of applications where these properties are required. For example, automobile airbags require flame retardancy, durability, and flexibility, so composite materials in which a coating layer made of silicone resin is formed on a fiber fabric are used as materials for these airbags. Furthermore, composite materials in which a coating layer made of silicone resin is formed on a substrate such as paper are used as release sheets and release tapes.

[0003] On the other hand, to protect the global environment, there is a demand for degradable polymers that can be easily decomposed. Patent Documents 1 and 2 describe pressure-sensitive adhesive compositions comprising polymers having a hydrazine structure. These pressure-sensitive adhesive compositions are stable in air but are rapidly decomposed by reaction with an oxidizing agent such as sodium hypochlorite.

[0004] JP 2013-037067 A JP 2013-001692 A

[0005] An object of the present invention is to provide a laminate having an easily decomposable coating layer while retaining the properties inherent in a siloxane structure, such as sliding properties, releasability, stain resistance, chemical resistance, heat resistance, cold resistance, flexibility, and electrical insulation.

[0006] The present inventors have found that the above problems can be solved by using a crosslinked product containing a siloxane structure that can be decomposed by an oxidizing agent, and have completed the present invention.

[0007] That is, the present invention includes the following aspects. <1> A laminate comprising a substrate and a coating layer formed on the substrate, the coating layer being made of a crosslinked product containing a siloxane structure that can be decomposed by an oxidizing agent. <2> The laminate according to item 1, wherein the crosslinked product has a hydrazine structure represented by formula (1). -A １ -NH-NH-A ２ - (1) (In formula (1), A １ , A ２ are each a carbonyl group or a single bond, and A １and A ２ at least one of the groups is a carbonyl group.) <3> The laminate according to item 1 or 2, wherein the substrate is a film, a woven fabric, or a nonwoven fabric. <4> The laminate according to any one of items 1 to 3, wherein the substrate is made of a polyester resin, a polyurethane resin, a polyamide resin, or cellulose. <5> The laminate according to any one of items 1 to 4, wherein the burning rate in a flammability test based on FMVSS No. 302 is 105 mm / min or less. <6> The laminate according to any one of items 1 to 5, wherein an adhesive layer made of a (meth)acrylic resin or a polyurethane resin is provided on the coating layer. <7> The laminate according to item 6, wherein the peel strength between the coating layer and the adhesive layer is 2.0 N / 50 mm or less. <8> A crosslinkable composition for obtaining a crosslinked product containing a siloxane structure decomposable by an oxidizing agent. <9> The crosslinkable composition according to item 8, wherein the crosslinkable composition contains a crosslinking agent having a hydrazine structure represented by formula (1). -A １ -NH-NH-A ２ - (1) (In formula (1), A １ , A ２ are each a carbonyl group or a single bond, and A １ and A ２ At least one of the groups is a carbonyl group.) <10> The crosslinkable composition according to item 8 or 9, containing a crosslinking agent represented by formula (2). (In formula (2), n≧0, k≧0, m≧0, p1≧1, p2≧1, p3≧1. R １ , R ２ , R ３ are each independently a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a heteroatom. １ is a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. ２ is a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. １ ~A ８ is a carbonyl group or a single bond, and A １ and A ２ At least one of A is a carbonyl group, ３and A ４ At least one of A is a carbonyl group, ５ and A ６ At least one of A is a carbonyl group, ７ and A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３ are each independently a reactive functional group, hydrogen, or halogen. １ , Q ２ , Q ３ are each independently at least one selected from the group consisting of a thiol group, a carboxyl group, a vinyl group, an alkynyl group, an allyl group, an acrylate group, and a methacrylate group. <12> The crosslinkable composition according to any one of items 8 to 11, further comprising a curable resin having a hydrosilyl group. <13> The crosslinkable composition according to any one of items 8 to 12, further comprising an iron complex. <14> A method for decomposing a laminate, comprising a step of contacting the laminate according to any one of items 1 to 7 with an aqueous solution containing an oxidizing agent at 100°C or less.

[0008] The laminate of the present invention can reduce the burden on the global environment while maintaining the properties inherent in the siloxane structure, such as sliding properties, releasability, stain resistance, chemical resistance, heat resistance, cold resistance, flexibility, and electrical insulation.

[0009] <<Laminate>> The laminate of the present invention includes a substrate and a coating layer formed on the substrate, and is characterized in that the coating layer comprises a crosslinked material containing a siloxane structure that is decomposable by an oxidizing agent.

[0010] <Substrate> Examples of materials for the substrate constituting the laminate include synthetic resins, natural materials, carbon materials, glass, etc. These materials may be used alone or in combination of two or more.

[0011] Examples of synthetic resins include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate, polybutylene naphthalate, polylactic acid, polyhydroxybutyric acid, polybutylene succinate, polycaprolactone, polyhydroxyalkanoic acid, and polyglycolic acid; polyamide resins such as nylon 6, nylon 6,6, and aramid; polyolefin resins such as polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, and cyclic olefin resin; vinyl resins such as polyvinyl chloride and polyvinylidene chloride; polyurethane resin, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyethersulfone (PES) resin, polycarbonate (PC) resin, polyimide resin, acrylic resin, and triacetyl cellulose (TAC) resin. Examples of natural materials include cellulose, cotton, and wool. Examples of carbon materials include carbon nanofibers and cellulose nanofibers. Among these, polyester resins, polyurethane resins, polyamide resins, and cellulose are preferred.

[0012] The structure of the laminate is not particularly limited as long as a coating layer can be formed thereon, and examples thereof include film, woven fabric, nonwoven fabric, paper, etc. The thickness of the substrate is not particularly limited, but is preferably 1 μm to 5 mm, more preferably 5 μm to 1 mm, and even more preferably 10 μm to 500 μm.

[0013] <Coating Layer> The coating layer is formed on a substrate and is made of a crosslinked material containing a siloxane structure that can be decomposed by an oxidizing agent. The crosslinked material that constitutes the coating layer is not particularly limited in composition as long as it contains a siloxane structure and is decomposed by reaction with an oxidizing agent. Examples include crosslinked materials of polymers having a hydrazine structure or an azo structure that are easily decomposed by reaction with an oxidizing agent. Crosslinked materials having a hydrazine structure are preferred in terms of excellent adhesion to the substrate. Note that the hydrazine structure can also be converted to an azo structure by a controlled oxidation reaction.

[0014] The crosslinked material constituting the coating layer preferably contains 40% by weight or more, and more preferably 60% by weight or more, of a siloxane structure in order to exhibit functions such as sliding properties, releasability, antifouling properties, and chemical resistance. Furthermore, the crosslinked material constituting the coating layer preferably contains 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight, of a hydrazine structure or an azo structure in order to exhibit easy dismantling properties. The amount of each component can be confirmed, for example, by a method of calculation using spectroscopic analysis such as FT-IR, or by a method of calculation using NMR or HPLC after decomposition in an aqueous solution containing an oxidizing agent.

[0015] The crosslinked material constituting the coating layer is preferably a crosslinked material containing a hydrazine structure, and more preferably a crosslinked material containing a hydrazine structure represented by formula (1). １ -NH-NH-A ２ - (1) In formula (1), A １ , A ２ are each a carbonyl group or a single bond, and A １ and A ２ At least one of A is a carbonyl group. １ and A ２ When one of the groups is a carbonyl group, it has the advantage of being easily decomposed with an oxidizing agent. １ and A ２ When both of the groups are carbonyl groups, there is an advantage that the decomposition products are easily dissolved in a solution.

[0016] The coating layer is formed, for example, by a method including a step of applying a crosslinkable composition to a substrate and a step of crosslinking the applied crosslinkable composition. The crosslinkable composition is not particularly limited in composition as long as the crosslinked product described above can be obtained by a crosslinking reaction in the composition, but it preferably contains a crosslinking agent containing a hydrazine structure. As the crosslinking agent containing a hydrazine structure, a crosslinking agent containing a hydrazine structure represented by the above formula (1) is preferred, and a crosslinking agent represented by formula (2) is more preferred. In formula (2), n≧0, k≧0, m≧0, p1≧1, p2≧1, and p3≧1. R １ , R ２ , R ３are each independently a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a heteroatom. １ is a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. ２ is a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. １ ~A ８ is a carbonyl group or a single bond, and A １ and A ２ At least one of A is a carbonyl group, ３ and A ４ At least one of A is a carbonyl group, ５ and A ６ At least one of A is a carbonyl group, ７ and A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３ are each independently a reactive functional group, or hydrogen or halogen.

[0017] In the narrow sense, the term "crosslinking agent" may refer to a chemical substance that forms chemical bonds between polymers or within a polymer. In this specification, however, the term "crosslinking agent" encompasses not only chemical substances that form chemical bonds between polymers or within a polymer, but also chemical substances that can form chemical bonds between their own molecules.

[0018] <n, m, k in formula (2)> In formula (2), n and m are all 0 or more, but each independently is preferably 1 or more, more preferably 2 or more. When n is 1 or more, the compound has two or more hydrazine structures (-A-NH-NH-A-), thereby improving decomposition properties. There are no particular upper limits for n and m, but they can each be 50 or less.

[0019] In formula (2), k is 0 or more, preferably 1 or more, and more preferably 2 or more. When k is 1 or more, the crosslinkable composition containing the crosslinking agent can undergo three-dimensional crosslinking. The upper limit of k is not particularly limited, but can be 50 or less.

[0020] <R in formula (2) １ , R ２ , and R ３ > R １ , R ２ , and R ３ are each independently a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a heteroatom.

[0021] The divalent group containing a siloxane structure contains an —Si—O— bond as a main skeleton. The main skeleton may be a linear structure, a branched structure, or a cyclic structure. The number of silicon atoms in the divalent group containing a siloxane structure is preferably 2 to 400, more preferably 4 to 200, and even more preferably 8 to 150.

[0022] In the siloxane structure, the hydrogen atoms bonded to the silicon atoms may be substituted. Specific examples of the substituent include alkyl groups, alkoxy groups, phenoxy groups, halogen atoms, amino groups, sulfo groups, cyano groups, and nitro groups.

[0023] Specific examples of divalent groups containing a siloxane structure include dimethyl silicone, diethyl silicone, ethyl methyl silicone, polymethyl silsesquioxane, and modified silicones obtained by modifying the hydrocarbon groups at the ends and / or side chains of these groups to contain heteroatoms such as N, S, O, and P.

[0024] R １ , R ２ , and R ３ When is a hydrocarbon group, in order to achieve a good decomposition rate and solvent solubility, the number of carbon atoms therein is preferably 1 to 600, more preferably 3 to 100, and even more preferably 4 to 50. The hydrocarbon group may be a saturated or unsaturated hydrocarbon group, and may have any of a linear structure, a branched structure, and a cyclic structure.

[0025] The hydrocarbon group may have a substituent, specific examples of which include an alkoxy group, a phenoxy group, a halogen atom, an amino group, a sulfo group, a cyano group, and a nitro group.

[0026] The hydrocarbon group may contain heteroatoms. When heteroatoms are contained, the number thereof is preferably 1 to 300. The heteroatoms may be present in the main chain of the hydrocarbon group or in the side chain. Examples of heteroatoms include N, S, O, and P. Examples of structures containing heteroatoms contained in the hydrocarbon group include: The hydrocarbon group may not contain a heteroatom.

[0027] Specific examples of the hydrocarbon group include linear hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, ether, urethane, urea, ester, thioether, carbonate, and amide, branched hydrocarbons such as isopropylene, isobutylene, 2,2-dimethylpropylene, and 2-ethyl-2-methylpropylene, cyclic hydrocarbons such as cyclohexylene, cyclopentylene, norbornenylene, phenylene, and naphthylene, PEG chains, and trivalent or tetravalent groups formed from these groups. The hydrogen atoms of these hydrocarbon groups may be substituted with the aforementioned substituents.

[0028] <Z in formula (2) １ and Z ２ > In formula (2), Z １ Z is a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. ２ is a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom.

[0029] In formula (2), Z １ is a group containing a siloxane structure, Z １ is divalent when k=0, and is trivalent or more when k≧1. ２ When is a group containing a siloxane structure, its valency is divalent.

[0030] The group containing a siloxane structure contains an —Si—O— bond as a main skeleton. The main skeleton may be a linear structure, a branched structure, or a cyclic structure. The number of silicon atoms in the group containing a siloxane structure is preferably 2 to 400, more preferably 4 to 200, and even more preferably 8 to 150.

[0031] In the siloxane structure, the hydrogen atoms bonded to the silicon atoms may be substituted. Specific examples of the substituent include alkyl groups, alkoxy groups, phenoxy groups, halogen atoms, amino groups, sulfo groups, cyano groups, and nitro groups.

[0032] Specific examples of groups containing a siloxane structure include dimethyl silicone, diethyl silicone, ethyl methyl silicone, polymethyl silsesquioxane, and modified silicones obtained by modifying the hydrocarbon groups at the terminals and / or side chains of these groups to contain heteroatoms such as N, S, O, and P.

[0033] Z １ and Z ２ When is a hydrocarbon group, in order to achieve a good decomposition rate and solvent solubility, the number of carbon atoms therein is preferably 1 to 700, more preferably 3 to 300, and even more preferably 5 to 100. The hydrocarbon group has a saturated or unsaturated hydrocarbon group as the main skeleton, and may have a linear structure, a branched structure, or a cyclic structure.

[0034] The hydrocarbon group may have a substituent, specific examples of which include an alkoxy group, a phenoxy group, a halogen atom, an amino group, a sulfo group, a cyano group, and a nitro group.

[0035] The hydrocarbon group may contain heteroatoms such as N, S, O, and P. When heteroatoms are contained, the number thereof is preferably 1 to 350. The heteroatoms may be present in the main chain of the hydrocarbon group or in the side chain. Examples of structures containing heteroatoms contained in the hydrocarbon group include: The hydrocarbon group may not contain a heteroatom.

[0036] The hydrocarbon group may have a reactive functional group, such as a hydroxyl group, an amino group, a hydrazide group, a thiol group, an isoprenyl group, a crotonamide group, a crotonate group, a carboxylic acid, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a hydroxysilyl group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a methylol group, a silanol group, or an alkoxysilyl group.

[0037] Specific examples of the hydrocarbon group include linear hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, ether, urethane, urea, ester, thioether, carbonate, and amide, branched hydrocarbons such as isopropylene, isobutylene, 2,2-dimethylpropylene, and 2-ethyl-2-methylpropylene, cyclic hydrocarbons such as cyclohexylene, cyclopentylene, norbornenylene, phenylene, and naphthylene, PEG chains, and trivalent or tetravalent groups formed from these groups. The hydrogen atoms of these hydrocarbon groups may be substituted with the aforementioned substituents.

[0038] Z １ and Z ２ The structures of Z are independent of each other and may be the same or different. １ and Z ２ There may be multiple Z １ , Z ２ may be the same or different from each other. １ and Z ２ When the structures of Z are different from each other, the decomposition property and solvent solubility of the crosslinked product can be controlled by selecting the combination of the structures. １ and Z ２ The following are examples of cases where the structures of Z are different from each other: １ and Z ２ Contains one or more of each. １ Includes 2 or more Z ２ Includes: Z １Contains one or more of Z ２ Contains two or more. １ Contains two or more of Z ２ The combination of two or more Z includes, for example, a combination of a Z having high water solubility in the decomposition product and a Z having low water solubility in the decomposition product. In addition, the characteristics before decomposition include a combination of a Z having a high molecular weight and a Z having a low molecular weight, a combination of a hydrophilic Z and a hydrophobic Z, a combination of a Z having a high polarity and a Z having a low polarity, and a combination of a Z having a flexible structure and a Z having a rigid structure.

[0039] The crosslinking agent represented by formula (2) is Z １ or Z ２ It is preferable that the ring structure does not contain two or more ring structures. １ or Z ２ This is because, when the compound has a cyclic structure containing two or more Z groups, the solvent solubility may decrease. １ or Z ２ The cyclic structure containing two or more of R １ , R ２ , R ３ , Z １ , Z ２ Examples of the ring structure include a ring structure formed by bonding two or more of the following to each other.

[0040] In formula (2), R １ , R ２ , R ３ , Z １ , Z ２ It is preferable that at least one selected from the group consisting of is a group containing a siloxane structure. This has the advantage of being able to impart properties such as sliding properties, releasability, antifouling properties, and chemical resistance to the crosslinked product, and also has the advantage of improving compatibility with other additives having a siloxane structure. １ , R ２ , R ３ , Z １ , Z ２ Preferably, at least two of the groups are groups containing a siloxane structure, and more preferably, at least three of the groups are groups containing a siloxane structure.

[0041] <Molecular weight of R and Z> In formula (2), R １ , R ２, and R ３ and / or Z １ and Z ２ Preferably, the molecular weight of at least one selected from the group consisting of is 200 or more. By adjusting the molecular weights of R and Z in this manner, the solubility of the crosslinking agent in a solvent can be improved. Furthermore, when a cured product is produced using the crosslinking agent, precipitation is suppressed, and a molded product with uniform composition and physical properties can be obtained.

[0042] R １ , R ２ , R ３ When two or more of any of R are present, only one of them may have a molecular weight of 200 or more. １ If there is one R １ The molecular weight of R may be 200 or more. １ , R ２ , and R ３ Preferably, the molecular weight of two or more selected from the group consisting of R １ , R ２ , and R ３ It is more preferable that the molecular weight of the copolymer is 200 or more.

[0043] Similarly, Z １ and Z ２ When two or more of any of Z are present, only one of them may have a molecular weight of 200 or more. １ and Z ２ It is preferable that the molecular weight of R is 200 or more. １ , R ２ , and R ３ and Z １ and Z ２ It is particularly preferred that at least one selected from the group consisting of has a molecular weight of 200 or more.

[0044] The molecular weight of R and Z is preferably 200 or more, more preferably 300 or more, even more preferably 700 or more, and even more preferably 900 or more. There is no particular upper limit to the molecular weight, but it is generally 10,000 or less. When the molecular weight is within this range, the solubility of the crosslinking agent in a solvent can be improved. １ , R ２ , R ３ , Z １ , Z ２ The molecular weight can be determined, for example, by contacting a crosslinking agent with an oxidizing agent and determining the molecular weight from the resulting decomposition product by GPC (gel permeation chromatography) or by determining the structure by NMR. When the molecular weight is determined by GPC (gel permeation chromatography), it is calculated as a weight average molecular weight (Mw).

[0045] In formula (2), it is preferable that n ≧ 1 and k ≧ 1. In this case, the crosslinking agent becomes branched, and three-dimensional crosslinking becomes possible. In formula (2), n ≧ 1 and k ≧ 1, and Z １ The molecular weight of Z is preferably 200 or more, more preferably 300 or more, and even more preferably 700 or more. １ as the main skeleton and is a branched compound having two or more hydrazine-derived structures (-A-NH-NH-A-) in the side chain, making three-dimensional crosslinking possible.

[0046] In order to complicate the structure of the crosslinking agent, suppress crystallization, and improve solubility in a solvent, n≧2, m≧2, or m≧1 and k≧2 in formula (2), and Z １ or Z ２ It is preferable that a plurality of Z １ or Z ２ It is preferable that the molecular weight of at least one of the groups is 200 or more. １ or Z ２ It is more preferable that one or more of the Z groups have a molecular weight of 200 or more. １ or Z ２ It is even more preferable that the molecular weight of at least one of the above is 300 or more, and particularly preferably 700 or more.

[0047] <Q in formula (2) １ , Q ２ , and Q ３ In formula (2), Q １ , Q ２ , Q ３ are each independently a reactive functional group, or hydrogen or halogen. １ , Q ２ , Q ３ are R １ , R ２ , R ３ It bonds to the hydrazine structure (-A-NH-NH-A-) via

[0048] Examples of reactive functional groups include thiol groups, carboxyl groups, vinyl groups, alkynyl groups, allyl groups, acrylate groups, methacrylate groups, hydroxyl groups, amino groups, hydrazide groups, acid anhydride groups, crotonate groups, isoprenyl groups, acrylamide groups, methacrylamide groups, crotonamide groups, epoxy groups, oxetane groups, oxazoline groups, isocyanate groups, carbodiimide groups, methylol groups, silanol groups, hydroxysilyl groups, alkoxysilyl groups, etc. Among these, thiol groups, vinyl groups, alkynyl groups, allyl groups, acrylate groups, and methacrylate groups are preferred because the crosslinking reaction proceeds under film-forming conditions suitable for the production process of release films, release papers, and airbags.

[0049] p1, p2, and p3 are each Q contained in the crosslinking agent １ , Q ２ , Q ３ p1, p2, and p3 each represent a number of 1 or more, but each independently represents a number of 1 to 4, and more preferably 1 or 2. １ , Q ２ , Q ３ is a reactive functional group and p1, p2, and p3 are 2 or more, three-dimensional crosslinking becomes easy, and the strength and reliability of the crosslinked product are improved. １ Comrade, Q ２ Peer or Q ３When the reactive functional groups are different from each other, it becomes easy to select various types of curable resins and crosslinking processes. Furthermore, when only specific reactive functional groups are crosslinked, the reactive functional groups not used in the crosslinking reaction can contribute to improving adhesion and solubility. When p1 = 1, p2 = 1, or p3 = 1, the decomposition rate is likely to be improved.

[0050] Q １ , Q ２ , Q ３ may be, independently of each other, hydrogen or a halogen, including fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0051] <A in formula (2) １ ~A ８ > A １ ~A ８ is a carbonyl group or a single bond. １ and A ２ At least one of A is a carbonyl group, ３ and A ４ At least one of A is a carbonyl group, ５ and A ６ At least one of A is a carbonyl group, ７ and A ８ At least one of the two A's on either side of -NH-NH- is a carbonyl group. When one of them is a carbonyl group, it is easily decomposed by an oxidizing agent. When both are carbonyl groups, the decomposition product is easily dissolved in a solution containing an oxidizing agent.

[0052] The crosslinking agent preferably has a weight average molecular weight of 300 to 30,000, more preferably 400 to 5,000. When the molecular weight is within this range, it becomes easy to adjust the crosslink density and solvent solubility.

[0053] The crosslinking agent is preferably liquid at 30 to 60° C., and more preferably liquid at 20 to 120° C. In this case, it has excellent miscibility with other components when preparing the crosslinkable composition, and can prevent precipitation of other components during molding.

[0054] <Method for Synthesizing Crosslinking Agent Having a Hydrazine Structure> A method for synthesizing a crosslinking agent having a hydrazine structure is not particularly limited, and a crosslinking agent in which carbonyl groups are present on both sides of —NH—NH— can be obtained, for example, by reacting a hydrazide compound, semicarbazide compound, or carbazate compound with a carbonate compound, an isocyanate compound, an acid anhydride, an acid halide, or a cyclic ester compound; a reaction between hydrazine and a carboxylic acid ester; a reaction between hydrazine and a carbonate compound; or a reaction between hydrazine and an isocyanate compound.

[0055] Furthermore, a crosslinking agent in which a carbonyl group is present on one side of -NH-NH- can be obtained by, for example, reacting a hydrazide compound, a semicarbazide compound, or a carbazate compound with a compound having an unsaturated double bond such as an acrylate or a methacrylate, an epoxy compound, an oxetane compound, or cyanuric acid chloride; or by reacting a hydrocarbon having a hydrazino group with a carbonate compound, an isocyanate compound, an acid anhydride, an acid halide, or a cyclic ester compound.

[0056] Examples of hydrazide compounds used in the above synthesis method include lactic acid hydrazide, methacrylic acid hydrazide, sebacic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, salicylic acid dihydrazide, and trimellitic acid trihydrazide. Examples of carbonate compounds include allyl N-succinimidyl carbonate and C,C'-(oxydi-2,1-ethanediyl)bisN-succinimidyl carbonate. Examples of isocyanate compounds include 2-isocyanatoethyl methacrylate, hexamethylene diisocyanate, toluene diisocyanate, and polymethylene polyphenyl polyisocyanate. Examples of semicarbazide compounds include N-allylhydrazinecarboxamide, N,N'-1,6-hexanediylbis[hydrazinecarboxamide], 4,4'-isophoronebis(semicarbazide), and 4,4'-(1,3-phenylenebismethylene)bis(semicarbazide). Examples of carbazate compounds include allylcarbazate and C,C'-(oxydi-2,1-ethanediyl)biscarbazate. Examples of acid anhydrides include methacrylic anhydride, succinic anhydride, and pyromellitic dianhydride. Examples of acid halides include acrylic acid chloride, sebacic acid dichloride, adipic acid dichloride, phthalic acid dichloride, salicylic acid dichloride, and trimesic acid trichloride. Examples of cyclic ester compounds include propiolactone, butyrolactone, valerolactone, etc. Examples of carboxylic acid esters include ethyl lactate, methylparaben, monomethyl succinate, diethyl adipate, trimethyl trimellitate, etc.

[0057] The laminate of the present invention tends to be less prone to combustion because it includes a coating layer made of a crosslinked material containing a siloxane structure. The flammability of the laminate can be evaluated by the method specified in FMVSS (Federal Motor Vehicle Safety Standards) No. 302. The laminate of the present invention preferably has a burning rate of 105 mm / min or less, more preferably 80 mm / min or less, and even more preferably 50 mm / min or less in a flammability test based on FMVSS No. 302.

[0058] <Adhesive Layer> The laminate may include an adhesive layer on the coating layer. The thickness of the adhesive layer is not particularly limited, but is preferably 5 to 100 μm. The adhesive layer is formed using an adhesive composition containing an adhesive. Examples of adhesives include (meth)acrylic resins obtained by homopolymerizing or copolymerizing (meth)acrylic acid ester monomers, polyurethane resins obtained by polyaddition of polyols and polyisocyanates, ethylene / vinyl acetate copolymer resins, silicone resins such as silicone rubber having a dimethylsiloxane skeleton, natural rubber, rubber-based resins such as styrene-isoprene-styrene block copolymers (SIS block copolymers), styrene-butadiene-styrene block copolymers (SBS block copolymers), styrene-ethylene-butylene-styrene block copolymers (SEBS block copolymers), styrene-butadiene rubber, polybutadiene, polyisoprene, polyisobutylene, butyl rubber, and chloroprene rubber. Among these, (meth)acrylic resins and polyurethane resins are preferred because of their excellent chemical stability, high flexibility in chemical structure design, excellent transparency, and ease of adjusting adhesive strength.

[0059] In addition to the adhesive, the pressure-sensitive adhesive composition may contain a crosslinking agent, a silane coupling agent, a surfactant, a solvent, and the like. Examples of crosslinking agents that can be used include polyfunctional metal chelates and organic crosslinking agents. Polyfunctional metal chelates are those in which a polyvalent metal is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Examples of atoms in the organic compound that form covalent or coordinate bonds include oxygen atoms. Examples of organic compounds include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds. Examples of organic crosslinking agents include isocyanate-based, peroxide-based, epoxy-based, and imine-based organic crosslinking agents. The content of the crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.01 to 10 parts by weight per 100 parts by weight of the pressure-sensitive adhesive.

[0060] The peel strength between the coating layer and the adhesive layer is preferably 2.0 N / 50 mm or less, more preferably 1.1 N / 50 mm or less, and even more preferably 0.2 N / 50 mm or less. The peel strength can be measured by the method described in the Examples.

[0061] <<Crosslinkable Composition>> The crosslinkable composition is used to form a coating layer on a substrate, which is composed of a crosslinked product containing a siloxane structure that is decomposable by an oxidizing agent. Examples of such crosslinkable compositions include (i) crosslinkable compositions containing a component that is easily decomposable by an oxidizing agent, and (ii) crosslinkable compositions in which a structure that is easily decomposable by an oxidizing agent is formed in the molecular chain by a crosslinking reaction.

[0062] (i) In a crosslinkable composition containing a component that is easily decomposable by an oxidizing agent, the component that is easily decomposable by an oxidizing agent includes a crosslinking agent containing a hydrazine structure or an azo structure (azo group). A crosslinking agent containing a hydrazine structure represented by formula (1) is preferred, and a crosslinking agent represented by formula (2) is more preferred. In the crosslinkable composition, only one crosslinking agent containing a hydrazine structure may be used, or two or more crosslinking agents may be used in combination. The content of the crosslinking agent containing a hydrazine structure in the crosslinkable composition is preferably 1 to 99 wt %, more preferably 15 to 99 wt %, even more preferably 50 to 99 wt %, and particularly preferably 70 to 98 wt %, based on the total solids content. If the content is less than 1 wt %, the decomposition rate of the easily decomposable crosslinked material layer tends to decrease, and if it exceeds 99 wt %, it tends to be difficult to form a uniform film.

[0063] (ii) In a crosslinkable composition in which a structure readily decomposable by an oxidizing agent is formed in the molecular chain by a crosslinking reaction, examples of components that form a structure readily decomposable by an oxidizing agent include a crosslinking agent having a diazonio group, a crosslinking agent having a diazo group, a crosslinking agent having a hydrazino group, a crosslinking agent having a hydrazide group, a crosslinking agent having a semicarbazide group, and a crosslinking agent having a carbazate group. The content of these crosslinking agents in the crosslinkable composition is preferably 1 to 99 wt %, more preferably 15 to 99 wt %, even more preferably 50 to 99 wt %, and particularly preferably 70 to 98 wt % of the total solids content. If the content is less than 1 wt %, the decomposition rate of the readily decomposable crosslinked material layer tends to decrease, and if it exceeds 99 wt %, it tends to be difficult to form a uniform film.

[0064] The crosslinkable composition may contain a crosslinking agent having a diazonio group, a diazo group, a hydrazino group, a hydrazide group, a semicarbazide group, a carbazate group, or a hydrazine structure or azo structure, as well as a curable resin, a polymerization initiator, a solvent, a surfactant, a flame retardant, a stabilizer, a reinforcing agent, and the like.

[0065] <Curable Resin> When the crosslinkable composition contains a crosslinking agent having an azo group or a crosslinking agent containing a hydrazine structure, the curable resin is not particularly limited as long as it has a structure that reacts with the reactive functional group of the crosslinking agent to crosslink, and examples thereof include curable resins having a reactive functional group at their terminals, such as a hydrosilyl group, a mercapto group, a hydroxyl group, an amino group, a hydrazide group, a carboxylic acid, an acid anhydride group, a vinyl group, an allyl group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, an oxazoline group, an isocyanate group, a carbodiimide group, a methylol group, a silanol group, or an alkoxysilyl group.

[0066] When the crosslinkable composition contains a crosslinking agent having a hydrazino group, the curable resin is not particularly limited as long as it has a structure that crosslinks by a reaction with the hydrazino group to form a hydrazine structure represented by the formula (1), and examples thereof include curable resins having a reactive functional group at the end, such as a carbonate group, an isocyanate group, an acid anhydride group, or a cyclic ester group.

[0067] When the crosslinkable composition contains a crosslinking agent having a hydrazide group, a crosslinking agent having a semicarbazide group, or a crosslinking agent having a carbazate group, the curable resin is not particularly limited as long as it has a structure that crosslinks by reacting with these groups to form a hydrazine structure represented by formula (1), and examples of the curable resin include curable resins having a reactive functional group at their terminals, such as a carbonate group, an isocyanate group, an acid anhydride group, a cyclic ester group, an acrylate group, a methacrylate group, a crotonate group, an isoprenyl group, an acrylamide group, a methacrylamide group, a crotonamide group, an epoxy group, an oxetane group, or a cyanuric chloride group.

[0068] When the crosslinkable composition contains a crosslinking agent having a diazonio group or a crosslinking agent having a diazo group, the curable resin is not particularly limited as long as it has a structure that crosslinks by reacting with these groups to form an azo structure, and examples of such curable resins include curable resins having a reactive functional group containing an unsaturated double bond at the end, such as a phenoxy group, a phenol group, an anilino group, an aniline group, or a naphthol group.

[0069] The curable resin may have only one type of reactive functional group or may have two or more types of reactive functional groups, and the number of reactive functional groups present in the curable resin is preferably two or more.

[0070] The main skeleton of the curable resin is preferably a hydrocarbon group which may have a heteroatom, or a group containing a siloxane structure. The main skeleton of the hydrocarbon group may be saturated or unsaturated, and may have a linear structure, a branched structure, or a cyclic structure. The hydrocarbon group constituting the main skeleton of the curable resin may contain heteroatoms such as N, S, O, and P. When heteroatoms are contained, the number thereof is preferably 1 to 500. Examples of structures containing heteroatoms contained in the main skeleton of the curable resin include: and the like. The hydrocarbon group may not contain a heteroatom. The main skeleton of the group containing a siloxane structure may have a linear structure, a branched structure, or a cyclic structure. The number of silicon atoms in the group containing a siloxane structure is preferably 2 to 400, more preferably 4 to 200, and even more preferably 8 to 150.

[0071] Specific examples of the hydrocarbon group constituting the main skeleton of the curable resin include linear hydrocarbons such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, ether, urethane, urea, ester, thioether, carbonate, and amide, branched hydrocarbons such as isopropylene, isobutylene, 2,2-dimethylpropylene, and 2-ethyl-2-methylpropylene, cyclic hydrocarbons such as cyclohexylene, cyclopentylene, norbornenylene, phenylene, and naphthylene, PEG chains, and trivalent or tetravalent groups of these groups. The hydrogen atoms of these hydrocarbon groups may be substituted with the aforementioned substituents.

[0072] At least one of the crosslinking agent and the curable resin contained in the crosslinkable composition preferably contains a siloxane structure in its main skeleton, and it is more preferable that both the crosslinking agent and the curable resin contain a siloxane structure in their main skeleton. Examples of crosslinking agents containing a siloxane structure in their main skeleton include those represented by the formula (2) above, where R １ , R ２ , R ３, Z １ , Z ２ In one embodiment, the crosslinking agent is a crosslinking agent in which at least one of the above groups is a group containing a siloxane structure.

[0073] The total amount of the crosslinking agent containing a siloxane structure and the curable resin containing a siloxane structure in the total solid content of the crosslinkable composition is preferably 50 to 99 wt %, more preferably 70 to 99 wt %, and even more preferably 83 to 99 wt %. Within this range, the crosslinked product has excellent releasability, sliding properties, and chemical resistance.

[0074] The curable resin is preferably liquid at 40° C. or below, soluble in a water-soluble organic solvent, or soluble in an acid or alkaline aqueous solution. By using such a curable resin, the decomposition rate of the coating layer by an oxidizing agent can be improved.

[0075] The molecular weight of the curable resin is preferably 100 to 10,000, more preferably 200 to 5,000. The curable resin may be a thermosetting resin or a photocurable resin. The amount of the curable resin in the crosslinkable composition is preferably 0.1 to 95 wt %, more preferably 1 to 80 wt %, of the total solid content.

[0076] <Polymerization Initiator> The polymerization initiator is not particularly limited as long as it is a compound that can catalyze the crosslinking reaction of a crosslinking agent or a curable resin, and any of a thermal polymerization initiator, a photopolymerization initiator, and a curing catalyst can be used. Examples of the polymerization initiator include metal complexes such as iron complexes, cobalt complexes, iridium complexes, ruthenium complexes, and nickel complexes having, as a ligand, 8-(dialkylphosphino)-2-(2-pyridinyl)quinoline, α,α'-dialkyl-2,6-pyridine dimethanimine, 2,2':6',2'-terpyridine, or the like, which may have a substituent; radical generators such as alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds; oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzyl urethane compounds, and orthonitrobenzyl urethane compounds. base generators such as those listed above; acid generators such as onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, and sulfonic acid compounds; tin compounds such as dibutyltin dilaurate and dibutyltin diacetate; bismuth compounds such as bismuth octoate; titanium compounds such as tetraoctyl titanate and titanium ethylacetoacetate; zirconium compounds such as zirconium monoacetylacetate and zirconium tetraacetylacetate; amines such as triethylenediamine and 1,4-diazabicyclo[2.2.2]octane (DABCO); and platinum compounds such as chloroplatinic acid and alkenylsiloxane platinum complexes. The amount of polymerization initiator in the composition is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight, per 100 parts by weight of the total of the crosslinker and the curable resin.

[0077] A hydrosilylation reaction is preferred as a crosslinking reaction suitable for the production process of release films, release papers, airbags, etc. Iron complexes are preferred as polymerization initiators for hydrosilylation reactions because they are highly active and less susceptible to curing inhibition by hydrazine or azo structures. Specific examples include (ethoxy-κO)(2-ethylhexanoate-κO,κO')[8-[bis(1-methylethyl)phosphino-κP]-5-fluoro-2-(2-pyridinyl-κN)quinoline-κN]iron, (2,2-dimethylpropanoate-κO)(2,2-dimethylpropanoate-κO,κO')[8-[bis(1-methylethyl)phosphino-κP]-5-fluoro-2-(2-pyridinyl-κN)quinoline-κN]iron, and derivatives thereof. The iron complex may be added as it is, or an iron complex may be generated during the film formation process by adding a reducing agent or ligand such as sodium borohydride, a metal alkoxide, or a carboxylate to a precursor of the iron complex, for example, iron chloride, dichloro[8-[bis(1-methylethyl)phosphino-κP]-5-fluoro-2-(2-pyridinyl-κN)quinoline-κN]iron, or dichloro[N,N'-[(2,6-pyridinediyl-κN)diethylidene]bis[2,6-diethylbenzenamine-κN]]iron.

[0078] <Solvent> Examples of the solvent include water and organic solvents, such as ether solvents, amide solvents, hydrocarbon solvents, alcohol solvents, ester solvents, aldehyde solvents, ketone solvents, and solvents containing carbon atoms, such as solvents containing carbon atoms and hetero atoms.

[0079] Examples of ether-based solvents include propylene glycol monomethyl ether, anisole, 4-methylanisole, diisopropyl ether, diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, and tert-butyl methyl ether. Examples of amide-based solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of hydrocarbon-based solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, tert-butylbenzene, trifluoromethylbenzene, nitrobenzene, and chlorobenzene. Examples of alcohol-based solvents include methanol, ethanol, propanol, butanol, ethylene glycol, and propylene glycol monomethyl ether. Examples of ester-based solvents include ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. Examples of aldehyde-based solvents include formaldehyde and acetaldehyde. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of solvents containing a carbon atom and a heteroatom include acetonitrile and dimethyl sulfoxide. When the crosslinkable composition is applied to a woven fabric, a nonwoven fabric, paper, or the like, the blending amount of the solvent in the crosslinkable composition is preferably 1 to 99% by weight, more preferably 1 to 70% by weight, and even more preferably 1 to 30%. When the crosslinkable composition is applied to a film, the blending amount is preferably 1 to 99% by weight, more preferably 30 to 99% by weight, and even more preferably 70 to 99% by weight.

[0080] The solvents listed above may be used alone or in combination of two or more. The boiling point of the solvent is preferably 150°C or less, more preferably 130°C or less, and even more preferably 110°C or less. When the boiling point is within these ranges, the solvent can be removed by heating for a relatively short time. The amount of solvents having a boiling point of more than 150°C in the crosslinkable composition is preferably less than 10% by weight. In this range, the solvent can be removed at a relatively low temperature after the crosslinkable composition is applied to the substrate, allowing the use of substrates with low heat resistance.

[0081] <Surfactant> Examples of surfactants include siloxane-based compounds such as polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; polyether-based compounds such as polyoxyethylene alkylphenyl ether, propylene oxide polymer, and ethylene oxide polymer; carboxylic acids such as coconut oil fatty acid amine salts and gum rosin; ester-based compounds such as castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, and succinate esters; and sulfonate compounds such as alkylarylsulfonic acid amine salts and dioctyl sodium sulfosuccinate. The amount of the surfactant is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.1 to 5% by weight, based on the total solid content of the crosslinkable composition.

[0082] <Flame Retardant> Examples of flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; intumescent flame retardants such as melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate; brominated flame retardants such as polybrominated biphenyl, hexabromocyclododecane, and tetrabromobisphenol A; and organoaluminum compounds such as aluminum tris(acetylacetonate), aluminum tris(ethyl acetate), and aluminum isopropylate. The flame retardants listed above may be used alone or in combination of two or more. The amount of flame retardant is preferably 1 to 70 wt %, more preferably 5 to 50 wt %, of the total solids content of the crosslinkable composition.

[0083] <Stabilizer> Examples of the stabilizer include acetylene compounds such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; eneyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole, phosphines, mercaptans, and hydrazines. The amount of the stabilizer is preferably 0.001 to 10% by weight, and more preferably 0.01 to 5% by weight, of the total solids content of the crosslinkable composition.

[0084] <Reinforcing Agent> Examples of reinforcing agents include dry silica and precipitated silica. The surface of these reinforcing agents may be hydrophobized with an organosilicon compound such as organochlorosilane, organosilazane, organoalkoxysilane, or organohydrogenpolysiloxane. The amount of reinforcing agent is preferably 1 to 40 wt %, more preferably 5 to 30 wt %, of the total solids content of the crosslinkable composition.

[0085] <Method for Producing a Coating Layer> The easily decomposable crosslinked layer can be produced by laminating a crosslinkable composition on a substrate and crosslinking the crosslinkable composition. Examples of methods for laminating the crosslinkable composition on a substrate include coating and immersion. Specific examples of coating methods include bar coating, spin coating, spray coating, dip coating, nozzle coating, gravure coating, reverse roll coating, die coating, air doctor coating, blade coating, rod coating, curtain coating, knife coating, transfer roll coating, squeeze coating, impregnation coating, kiss coating, calendar coating, extrusion coating, screen printing, inkjet printing, flexographic printing, offset printing, pad printing, water transfer, pressure-sensitive transfer, and in-mold molding. Another method for forming a coating layer includes laminating a film or sheet made of a crosslinkable composition to a substrate. The crosslinkable composition may be laminated on only one side of the substrate, or on both sides simultaneously or sequentially. When laminating on both sides, the crosslinkable compositions laminated on both sides may be of the same composition or may be of different compositions.

[0086] The crosslinking method of the crosslinkable composition includes light irradiation and heating. When crosslinking by light irradiation, the crosslinking is performed at 100 to 2000 mJ / cm. ２ When crosslinking is performed by heating, the heating temperature is preferably 40 to 200° C., and more preferably 80 to 120° C. The heating time is preferably 0.5 to 180 minutes, and more preferably 0.5 to 10 minutes.

[0087] The thickness of the coating layer is not particularly limited, but is preferably 0.01 to 30 μm, and more preferably 0.05 to 20 μm. Within this range, both the strength of the coating layer and the rate of decomposition and removal by the oxidizing agent can be achieved. Furthermore, when the laminate is used as a release film, the thickness of the coating layer is preferably 0.01 to 2 μm, and more preferably 0.05 to 0.9 μm. When the laminate is used as release paper, the thickness of the coating layer is preferably 0.1 to 30 μm, and more preferably 0.3 to 9 μm. When the laminate is used as a component of an airbag, the thickness of the coating layer is preferably 0.5 to 30 μm, and more preferably 2 to 20 μm.

[0088] The coating layer may be formed directly or indirectly on the substrate. Furthermore, multiple coating layers may be laminated on the substrate. The multiple coating layers may have the same composition or different compositions. The coating layer may be present on at least a portion of the surface of the substrate, or may be present on the entire surface. Furthermore, the laminate may include, in addition to the coating layer, any layer such as a printing layer, a gas barrier layer, a receiving layer, a protective layer, or a filling layer. These layers are preferably soluble or dispersible in water, an acidic aqueous solution, an alkaline aqueous solution, acetone, alcohol, or other water-soluble organic solvent.

[0089] <<Method for Decomposing the Coating Layer>> The coating layer can be decomposed by contact with a solution containing an oxidizing agent. The crosslinked material constituting the coating layer is rapidly decomposed by the action of the oxidizing agent, peeled off from the substrate, and dispersed or dissolved in the solution. As a result, the substrate can be efficiently recovered.

[0090] <Decomposition of Easily Decomposable Crosslinked Product> The oxidizing agent used to decompose the coating layer is not particularly limited as long as it is an oxidizing agent other than molecular oxygen, and examples thereof include hypochlorites such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and ammonium hypochlorite; hypobromites such as ammonium hypobromite, calcium hypobromite, potassium hypobromite, and sodium hypobromite; isocyanuric acid chlorides such as chlorinated sodium isocyanurate, chlorinated potassium isocyanurate, chlorinated calcium isocyanurate, and chlorinated ammonium isocyanurate; peroxides such as hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, and perbenzoic acid; halogens such as chlorine, bromine, and iodine; and ozone. Among these, hypochlorous acid, hypochlorites, isocyanuric acid chlorides, hydrogen peroxide, or ozone are preferred, and water-soluble salts such as sodium hypochlorite and sodium hypobromite, and ozone water are more preferred. These oxidizing agents are preferably used by dissolving them in an aqueous solution. The solution containing the oxidizing agent may also contain alkali agents such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, and tetramethylammonium hydroxide, organic solvents such as ethanol, methanol, isopropanol, and tetrahydrofuran, and surfactants such as alkylbenzenesulfonates, alkyl sulfate ester salts, alkyl ether carboxylates, polyoxyethylene alkyl ethers, glycerin fatty acid esters, alkyltrimethylammonium salts, and alkylcarboxybetaines. The concentration of the oxidizing agent in the solution is preferably 0.001 to 50 wt %, more preferably 0.001 to 10 wt %, and even more preferably 0.01 to 3 wt %.

[0091] The temperature condition when contacting the coating layer with the solution containing an oxidizing agent is preferably 100°C or less, more preferably 15 to 50°C. The time condition is preferably 60 minutes or less, more preferably 10 minutes or less. If necessary, the solution may be shaken or stirred during the reaction with the oxidizing agent. The specific method for contacting the coating layer with the solution containing an oxidizing agent is not particularly limited, and examples include a method of immersing a laminate including the coating layer in a solution containing an oxidizing agent, and a method of spraying or dropping the solution containing an oxidizing agent onto the coating layer.

[0092] The crosslinked material that constitutes the coating layer is oxidized by contact with an oxidizing agent, and decomposed into N ２ , carboxylic acids, alcohols, amines, etc. may be produced. Specific examples of carboxylic acids include succinic acid, malonic acid, adipic acid, phthalic acid, trimellitic acid, and polyacrylic acid. Specific examples of alcohols include ethylene glycol, diethylene glycol, triethylene glycol, hexanediol, pentitol, pentaerythritol, polyethylene glycol, polyvinyl alcohol, resorcinol, and phenol novolac. Specific examples of amines include hexamethylenediamine, pentamethylenediamine, isophoronediamine, toluenediamine, and diaminodiphenylmethane. Decomposition products can be confirmed by NMR, IR spectra, etc.

[0093] After the step of contacting the laminate with the solution containing an oxidizing agent, fine solid components may be removed by centrifugation or filtration. Furthermore, solvent substitution, washing, etc. may also be performed. By undergoing these steps, a highly pure substrate can be recovered.

[0094] The present invention will be described below with reference to examples, but is not limited to the following examples. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

[0095] (1) Production of Laminate (Example 1) A crosslinkable composition B1 produced by mixing a crosslinking agent A1, a curable resin, a polymerization initiator, a solvent, and a surfactant in the weight ratios shown in Table 1 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and after drying at 120° C. for 2 minutes, a 500 mJ / cm ２ The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate C1 having a crosslinked layer with a thickness of 0.9 μm on the film.

[0096] Crosslinking agent A1 was produced by the following method. 10 g of a carbinol-modified polydimethylsiloxane (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.) with a molecular weight of approximately 1000, 16 g of acetone, and 6.5 g of triethylamine were mixed in a 100 ml recovery flask, and 6.0 g of di(N-succinimidyl) carbonate was added and stirred at room temperature overnight. 47 g of chloroform and 3.1 g of 4-pentenoic acid hydrazide were added to the reaction solution, and the mixture was stirred overnight at room temperature. This reaction solution was transferred to a separatory funnel, and 140 g of chloroform was added. The organic layer was then washed three times with 140 g of pure water. After washing, the organic layer was distilled off, yielding a crosslinking agent having the structure of formula (A1) in a 98% yield.

[0097] In the formula, R represents a hydrocarbon group.

[0098] 1H-NMR (CDCl ３ , δppm) 0.06 (76H, br, CH ３ ), 2.29-2.46 (8H, m, CH ２ CH ２ ), 4.96-5.10 (4H, m, CH=CH ２ ), 5.76-5.94 (2H, m, CH=CH ２ ), 7.74 (2H, br, NHNH), 8.41 (2H, br, NHNH)

[0099] The resulting crosslinking agent of formula (A1) was liquid at 30°C.

[0100] When a small amount of 20% aqueous sodium hypochlorite solution was added to the resulting crosslinking agent of formula (A1), foaming occurred, and the formation of 4-pentenoic acid as a decomposition product was confirmed by 1 H-NMR.

[0101] (Example 2) Crosslinkable composition B2, which was produced by mixing crosslinking agent A1, a curable resin, a polymerization initiator, and a solvent in the weight ratios shown in Table 2, was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and after drying at 120° C. for 2 minutes, 500 mJ / cm ２ The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate C2 having a crosslinked layer with a thickness of 0.9 μm on the film.

[0102] (Example 3) Crosslinkable composition B3 was prepared by mixing crosslinking agent A2, a curable resin, a polymerization initiator, a solvent, and a surfactant in the weight ratios shown in Table 3. The crosslinkable composition B3 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and dried at 120° C. for 10 minutes. After that, the crosslinkable composition B3 was subjected to a 2000 mJ / cm ２ The resulting crosslinked layer was cured with UV light at 1000 W / m, thereby producing a laminate C3 having a crosslinked layer with a thickness of 0.8 μm on the film. When the IR spectrum of the resulting crosslinked layer was confirmed, a peak at 810 cm originating from the unsaturated bond of the acrylate group was observed. －１ The peak at around 2560 cm originates from the thiol group －１ The decrease in the peak in the vicinity confirmed the formation of the structure of formula (D1).

[0103]

[0104] Crosslinking agent A2 was prepared by the following method. 2.0 g of 3-mercaptopropanehydrazide was dissolved in 26 g of THF in a 100 ml recovery flask, and 3.0 g of poly(hexamethylene diisocyanate) (Sigma-Aldrich) was added dropwise thereto, followed by stirring overnight at room temperature. The precipitated white solid was collected by decantation and dried in a vacuum dryer, yielding a crosslinking agent having the structure of formula (A2) in a yield of 94%.

[0105]

[0106] 1H-NMR (DMSO, δppm) 1.24-1.50 (24H, m, CH ２ ), 2.41 (6H, t, C=OCH ２ ), 2.67 (6H, t, SCH２ ), 2.97-3.10 (12H, m, NCH ２ ), 6.26 (3H, s, NH), 7.67 (3H, s, NH), 8.21 (2H, br, NH), 9.50 (3H, s, NH)

[0107] When a small amount of 20% aqueous sodium hypochlorite solution was added to the resulting crosslinking agent of formula (A2), foaming occurred, and the formation of 3-mercaptopropanoic acid as a decomposition product was confirmed by 1 H-NMR.

[0108] (Example 4) Crosslinkable composition B4 was prepared by mixing crosslinking agent A3, a curable resin, a polymerization initiator, a solvent, and a surfactant in the weight ratios shown in Table 4. The crosslinkable composition B4 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and dried at 120° C. for 10 minutes. After that, the crosslinkable composition B4 was subjected to a 2000 mJ / cm ２ The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate C4 having a crosslinked layer with a thickness of 0.8 μm on the film.

[0109] The IR spectrum of the resulting crosslinked layer was confirmed to be 810 cm , which is derived from the unsaturated bond of the acrylate group. －１ The peak at around 2560 cm originates from the thiol group －１ The decrease in the peak in the vicinity confirmed the formation of the structure of formula (D2).

[0110]

[0111]

[0112] Crosslinking agent A3 was prepared in the following manner. 11.1 g of poly(acrylic hydrazide) with a molecular weight of approximately 1,000 and 138 g of dimethyl sulfoxide were mixed in a 300 ml recovery flask, and 5.0 g of 2-isocyanatoethyl methacrylate was added dropwise at room temperature. After stirring for 4 hours, 10.6 g of succinic anhydride was added and stirred for an additional 2 hours. The reaction solution was added dropwise to 1,651 g of methyl isobutyl ketone, and the resulting solid was dried in a vacuum dryer at 50°C, yielding a crosslinking agent having the structure of formula (A3) in a 60% yield.

[0113]

[0114] 1 H-NMR (DMSO, δppm) 1.55 (20H, br, main chain CH ２ ), 2.11 (10H, br, main chain CH), 1.88 (9H, s, CH ３ ), 2.46 (28H, br, COCH ２ CH ２ CO), 3.47-3.51 (6H, m, NCH ２ ), 4.04-4.08 (6H, m, OCH ２ ), 5.67 (3H, d, C=CH ２ ), 6.06 (3H, d, C=CH ２ ), 6.43 to 6.52 (3H, m, CONHC), 9.82 (20H, br, NHNH), 12.12 (7H, br, COOH)

[0115] When a small amount of 20% aqueous sodium hypochlorite solution was added to the resulting crosslinking agent of formula (A3), foaming occurred, and the production of polyacrylic acid as a decomposition product was confirmed by 1 H-NMR.

[0116] (Example 5) Crosslinkable composition B5 was prepared by mixing crosslinking agent A4, a curable resin, a polymerization initiator, a solvent, and a surfactant in the weight ratios shown in Table 5. The crosslinkable composition B5 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and dried at 120° C. for 2 minutes. After that, the crosslinkable composition B5 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method. ２ The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate C5 having a crosslinked layer with a thickness of 0.5 μm on the film.

[0117]

[0118] Crosslinker A4 was prepared by the following method. 26.6 g of acrylate-modified polydimethylsiloxane (X-22-2445, manufactured by Shin-Etsu Chemical Co., Ltd.) with a molecular weight of approximately 3,200, 8.5 g of aluminum oxide (manufactured by Sigma-Aldrich), and 2.0 g of 3-mercaptopropanehydrazide were mixed in a 100 ml recovery flask and stirred at 50°C for 4 hours. 2.0 g of 3-mercaptopropanehydrazide and 20 g of toluene were added to the reaction solution, and the mixture was stirred overnight at 50°C. The aluminum oxide was then removed using a centrifuge. The resulting solution was concentrated using an evaporator, and then 130 g of chloroform and 60 g of pure water were added to perform a liquid separation operation. The lower layer was collected, and the solvent was removed using an evaporator, yielding a decomposable compound having the structure of formula (A4) in a yield of 67%.

[0119] In the formula, R represents a hydrocarbon group.

[0120] 1H-NMR (CDCl ３ , δppm) 0.08 (245H, br, CH ３ ), 2.46 (4H, t, C=OCH ２ ), 2.61 (4H, t, C=OCH ２ ), 2.79-2.86 (8H, m, CH ２ ), 3.89 (2H, br, NH), 7.01 (2H, br, NH)

[0121] The resulting decomposable compound of formula (A4) was liquid at 40°C.

[0122] When a small amount of 20% aqueous sodium hypochlorite solution was added to the obtained decomposable compound of formula (A4), foaming occurred, and the production of the decomposition product, 3-mercaptopropanoic acid, was confirmed by 1 H-NMR.

[0123] Comparative Example 1: 10 g of a thermosetting addition silicone composition KS-847T (manufactured by Shin-Etsu Polymer Co., Ltd., solids content 30 wt%) and 0.3 g of a platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Polymer Co., Ltd.) were mixed with n-hexane to prepare a 4 wt% crosslinkable composition E1. This crosslinkable composition was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by bar coating, dried at 120° C. for 2 minutes, and then subjected to a 500 mJ / cm ２The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate F1 having a crosslinked layer with a thickness of 0.2 μm on the film.

[0124] (Comparative Example 2) Crosslinkable composition E2 was prepared by mixing crosslinking agent A2, crosslinking agent A3, a polymerization initiator, a solvent, and a surfactant in the weight ratios shown in Table 6. The crosslinkable composition E2 was applied to a PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) by a bar coating method, and dried at 120° C. for 10 minutes. After that, the crosslinkable composition E2 was subjected to a 2000 mJ / cm ２ The resulting composition was cured with UV light at 1000 kJ / s to prepare a laminate F2 having a crosslinked layer with a thickness of 0.9 μm on the film.

[0125]

[0126] (2) Evaluation of Laminates (2-1) Chemical Resistance Test The surface of the laminates prepared in each Example and Comparative Example was wiped with a nonwoven fabric soaked in water or ethanol, and evaluated according to the following criteria: ○: No peeling of the silicone layer ×: Peeling of the silicone layer

[0127] (2-2) Recovery Test The laminates prepared in each Example and Comparative Example were immersed in a solution containing an oxidizing agent at room temperature for 5 minutes. After that, the solution was drained, and the substrates recovered were subjected to a peel strength test using Nitto 31B tape (19 mm wide). Dismantling ability was calculated using the following formula: Dismantling ability = peel strength of recovered substrate ÷ peel strength of substrate

[0128] A dismantling property of 0.8 or more was judged to be acceptable, and one less than 0.8 was judged to be unacceptable. The following solutions a and b were used as solutions containing oxidizing agents. (Solution a) A solution obtained by diluting Kitchen Haiter, manufactured by Kao Corporation, containing sodium hypochlorite, five times with Solmix AP-1, manufactured by Japan Alcohol Sales Co., Ltd., whose main ingredient is ethanol. (Solution b) A solution obtained by diluting Kitchen Haiter, manufactured by Kao Corporation, containing sodium hypochlorite, five times with propylene glycol monomethyl ether.

[0129] (2-3) Peel Strength Test: Nitto 31B tape (19 mm wide) was attached to the laminate prepared in each Example and Comparative Example. The tape was peeled off at an angle of 180° using a Strograph E-L to measure the peel strength.

[0130]

[0131] Comparative Example 1 failed the dismantling test in the recovery test. This is presumably because the coating layer did not contain a crosslinked material that can be decomposed by an oxidizing agent. Comparative Example 2 had a high peel strength. This is presumably because the crosslinked material that constitutes the coating layer did not contain a siloxane structure. Examples 1 to 5 passed the dismantling test in the recovery test, but had low peel strength.

Claims

1. A laminate comprising a substrate and a coating layer formed on the substrate, wherein the coating layer is made of a crosslinked material containing a siloxane structure that can be decomposed by an oxidizing agent.

2. The laminate according to claim 1, wherein the crosslinked product has a hydrazine structure represented by formula (1). １ -NH-NH-A ２ - (1) (In formula (1), A １ , A ２ are each a carbonyl group or a single bond, and A １ and A ２ At least one of the groups is a carbonyl group.

3. The laminate according to claim 1 or 2, wherein the substrate is a film, a woven fabric, or a nonwoven fabric.

4. The laminate according to any one of claims 1 to 3, wherein the substrate is made of a polyester resin, a polyurethane resin, a polyamide resin, or cellulose.

5. The laminate according to any one of claims 1 to 4, which has a burning rate of 105 mm / min or less in a flammability test based on FMVSS No.

302.

6. The laminate according to any one of claims 1 to 5, which comprises an adhesive layer made of a (meth)acrylic resin or a polyurethane resin on the coating layer.

7. The laminate according to claim 6, wherein the peel strength between the coating layer and the adhesive layer is 2.0 N / 50 mm or less.

8. A crosslinkable composition for obtaining a crosslinked product containing a siloxane structure that can be decomposed by an oxidizing agent.

9. The crosslinkable composition according to claim 8, which contains a crosslinking agent having a hydrazine structure represented by formula (1). １ -NH-NH-A ２ - (1) (In formula (1), A １ , A ２ are each a carbonyl group or a single bond, and A １ and A ２ At least one of the groups is a carbonyl group.

10. The crosslinkable composition according to claim 8 or 9, which contains a crosslinking agent represented by formula (2). (In formula (2), n≧0, k≧0, m≧0, p1≧1, p2≧1, p3≧1. R １ , R ２ , R ３ are each independently a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a heteroatom. １ is a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. ２ is a divalent group containing a siloxane structure, or a hydrocarbon group which may have a substituent or a hetero atom. １ ~A ８ is a carbonyl group or a single bond, and A １ and A ２ At least one of A is a carbonyl group, ３ and A ４ At least one of A is a carbonyl group, ５ and A ６ At least one of A is a carbonyl group, ７ and A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３ are each independently a reactive functional group, or hydrogen or halogen.

11. Q １ , Q ２ , Q ３ are each independently at least one selected from the group consisting of a thiol group, a carboxyl group, a vinyl group, an alkynyl group, an allyl group, an acrylate group, and a methacrylate group.

12. The crosslinkable composition according to any one of claims 8 to 11, further comprising a curable resin having a hydrosilyl group.

13. The crosslinkable composition according to any one of claims 8 to 12, further comprising an iron complex.

14. A method for decomposing a laminate, comprising the step of contacting the laminate according to any one of claims 1 to 7 with an aqueous solution containing an oxidizing agent at 100°C or lower.

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