Decomposing solution for decomposing oxidatively decomposable molded products

Abstract

The present invention provides a decomposing solution capable of decomposing oxidatively decomposable molded products in a short time. The present invention relates to a decomposing solution for decomposing oxidatively decomposable molded products, the decomposing solution containing an organic solvent, an oxidizing agent, and water.

Description

Decomposition liquid for decomposing oxidatively decomposable molded products

[0001] The present invention relates to a decomposition liquid for decomposing oxidatively decomposable molded articles.

[0002] Due to their moldability, durability, and light weight, plastic products are used in a variety of fields, such as daily necessities, automobiles, and electronic devices. However, they suffer from the problem of being difficult to decompose after disposal. In recent years, efforts have been made to develop degradable polymers that can be easily decomposed in order to protect the global environment. As one type of degradable polymer, polymers crosslinked with hydrazine derivatives have been disclosed (see Patent Documents 1 and 2). These polymers have a diacylhydrazine structure, and therefore exist stably in air, but are rapidly decomposed by reaction with an oxidizing agent such as sodium hypochlorite.

[0003] However, when an oxidatively decomposable molded product crosslinked with a hydrazine derivative is decomposed using a conventional decomposition solution, bubbles of nitrogen and other gases are generated and adhere to the surface of the molded product, preventing contact with the oxidizing agent and slowing down the decomposition rate.

[0004] JP 2011-236381 A International Publication No. 2021 / 131003

[0005] An object of the present invention is to provide a decomposition liquid capable of decomposing oxidatively decomposable molded products in a short period of time.

[0006] The present inventors have conducted extensive research into the components of the decomposition liquid and have found that adding an organic solvent to the decomposition liquid removes bubbles generated by the decomposition of oxidatively decomposable shaped bodies and swells the bodies, thereby improving the permeability of the oxidizing agent into the bodies, paper, and cloth, thereby enabling the oxidatively decomposable shaped bodies to be decomposed in a short period of time, thereby completing the present invention.

[0007] That is, the present invention includes the following aspects: <Item 1> A decomposition liquid for decomposing an oxidatively decomposable shaped product, the decomposition liquid comprising an organic solvent, an oxidizing agent, and water. <Item 2> The oxidatively decomposable shaped product is an oxidatively decomposable shaped product represented by the 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 A１ and A ２ Item 3: The decomposition liquid according to item 1, wherein the oxidatively decomposable shaped product contains a hydrazine structure represented by the following 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, and Z １ , Z ２ are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a heteroatom. １ ~A ８ is a carbonyl group or a single bond, and A １ ~A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３are each a reactive functional group independent of each other.) The decomposition liquid according to item 2 or 3, which is an oxidatively decomposable shaped product obtained by curing a hydrazine derivative represented by the formula: (Item 5) The decomposition liquid according to any one of items 1 to 4, wherein the oxidizing agent is hypochlorous acid, hypochlorite, isocyanuric acid chloride, hydrogen peroxide, or ozone. (Item 6) The decomposition liquid according to any one of items 1 to 5, wherein the concentration of the oxidizing agent is 0.001 to 3 mass%. (Item 7) The decomposition liquid according to any one of items 1 to 6, wherein the organic solvent is an alcohol, an amine, or an ether. (Item 8) The decomposition liquid according to any one of items 1 to 7, further comprising an alkaline agent. (Item 9) The decomposition liquid according to any one of items 1 to 8, further comprising a surfactant. (Item 10) The decomposition liquid according to any one of items 1 to 9, wherein at least a portion of the oxidatively decomposable shaped product is covered with paper, woven fabric, or nonwoven fabric. (Item 11) A method for decomposing an oxidatively decomposable shaped product, comprising the step of contacting the oxidatively decomposable shaped product with the decomposition liquid according to any one of items 1 to 10. <Item 12> The method for decomposing oxidatively decomposable shaped products according to Item 11, wherein the decomposition liquid is circulated within the system in the contacting step. <Item 13> The method for decomposing oxidatively decomposable shaped products according to Item 11 or 12, wherein the oxidatively decomposable shaped products are shaken in the contacting step. <Item 14> The method for decomposing oxidatively decomposable shaped products according to Item 11 or 12, wherein the surface of the oxidatively decomposable shaped products is rubbed with fibers impregnated with the decomposition liquid in the contacting step.

[0008] The decomposition liquid of the present invention removes bubbles generated by the decomposition of oxidatively decomposable shaped bodies, swells the shaped bodies, and improves the permeability of the oxidizing agent into the shaped bodies, paper, and cloth, thereby enabling the oxidatively decomposable shaped bodies to be decomposed in a short period of time. While methods of increasing the concentration of the oxidizing agent are generally used to achieve decomposition in a short period of time, the decomposition liquid of the present invention enables decomposition in a short period of time even when the oxidizing agent concentration is low.

[0009] <<Decomposition Liquid>> The decomposition liquid for decomposing the oxidatively decomposable shaped article of the present invention is characterized by containing an organic solvent, an oxidizing agent, and water.

[0010] <Organic Solvent> The incorporation of an organic solvent causes the oxidatively decomposable molded product to swell, making it easier to supply the oxidizing agent to its interior, facilitating the dissolution of decomposition products produced by oxidative decomposition, and quickly removing bubbles generated during decomposition, thereby improving the decomposition rate of the oxidatively decomposable molded product. Furthermore, since the surface tension and viscosity of the decomposition liquid can be reduced, even when a substrate such as paper or cloth is laminated on the oxidatively decomposable molded product, the oxidizing agent can be quickly supplied to the oxidatively decomposable molded product, improving the decomposition rate of the laminate. Examples of organic solvents include ether-based solvents, amine-based solvents, amide-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ester-based solvents, aldehyde-based solvents, ketone-based solvents, and solvents containing carbon atoms, such as solvents containing carbon atoms and heteroatoms.

[0011] Examples of ether-based solvents include propylene glycol monomethyl ether, anisole, 4-methylanisole, diisopropyl ether, diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, tetrahydrofuran, isosorbide dimethyl ether, and dipropylene glycol dimethyl ether. Examples of amine-based solvents include monoethanolamine, diethanolamine, triethylamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, diglycolamine, and pyridine. 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, and tert-butylbenzene. Examples of alcohol-based solvents include methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol monomethyl ether, glycerin, diethylene glycol, and propylene glycol. 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-based solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of solvents containing carbon atoms and heteroatoms include acetonitrile, dimethyl sulfoxide, trifluoromethylbenzene, nitrobenzene, and chlorobenzene. These may be used alone or in combination of two or more. Among these, it is preferable that the organic solvent be water-soluble, and ether-based solvents, amine-based solvents, or alcohol-based solvents are more preferable, and alcohol-based solvents or ether-based solvents are even more preferable.

[0012] The content of the organic solvent in the decomposition liquid is not particularly limited, and is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and even more preferably 20 to 60% by mass. When the content is within the above range, efficient decomposition tends to be possible.

[0013] <Oxidizing Agent> The oxidizing agent is not particularly limited as long as it is an oxidizing agent other than molecular oxygen. Examples thereof include hypochlorites such as hypochlorous acid, 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 isocyanuric acid, chlorinated sodium isocyanurate, chlorinated potassium isocyanurate, chlorinated calcium isocyanurate, and chlorinated ammonium isocyanurate; halogenated hydantoin compounds such as chlorinated dimethylhydantoin, brominated dimethylhydantoin, chlorinated diethylhydantoin, brominated diethylhydantoin, chlorinated ethylmethylhydantoin, and brominated ethylmethylhydantoin; peroxides such as hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid, and perbenzoic acid; halogens such as chlorine, bromine, and iodine; and ozone. These may be used alone or in combination of two or more. Among these, hypochlorous acid, hypochlorite, isocyanuric acid chloride, and halogenated hydantoin compounds are preferred.

[0014] The content of the oxidizing agent in the decomposition liquid is not particularly limited, and is preferably 0.001 to 10% by mass, more preferably 0.001 to 3% by mass, and even more preferably 0.005 to 2% by mass. When the content is within the above range, efficient decomposition tends to be possible.

[0015] <Water> The content of water is not particularly limited, and is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, in the decomposition liquid. If the content exceeds 99% by mass, the effect of improving the decomposition rate by adding an organic solvent tends to be lost, and if the content is less than 1% by mass, it tends to be difficult to dissolve the oxidizing agent at a high concentration.

[0016] <Optional Components> The decomposition liquid may contain other components in addition to the organic solvent, oxidizing agent, and water, such as a surfactant, an alkaline agent, a chelating agent, and a thickener.

[0017] The incorporation of a surfactant improves the decomposition rate of the oxidatively decomposable molded product by facilitating the dispersion and removal of dirt adhering to the surface of the oxidatively decomposable molded product and decomposition products generated by oxidative decomposition, and by facilitating the rapid removal of bubbles generated during decomposition. Furthermore, the surface tension of the decomposition liquid can be adjusted, and even when a substrate such as paper or cloth is laminated on the oxidatively decomposable molded product, the oxidizing agent is quickly supplied to the oxidatively decomposable molded product, improving the decomposition rate of the laminate. 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; coconut oil fatty acid amine salt, gum methyl ester, ... Examples of surfactants include carboxylic acids such as sucralose, castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonates, and succinates; sulfonate compounds such as alkylarylsulfonic acid amine salts and dioctyl sodium sulfosuccinate; ammonium salt compounds such as dilauryldimethylammonium chloride, benzylmyristyldimethylammonium chloride, and cetylpyridinium chloride; and betaines such as alkyl betaine, fatty acid amidopropyl betaine, and 2-alkyl-N-carboxylmethyl-N-hydroxyethyl-imidazolinium betaine. When a surfactant is added, the amount added is preferably 0.01 to 7% by mass, and more preferably 0.02 to 5% by mass.

[0018] The incorporation of an alkaline agent facilitates the dissolution and removal of dirt adhering to the surface of the oxidatively decomposable shaped product and decomposition products such as carboxylic acids produced by oxidative decomposition, thereby increasing the decomposition rate of the oxidatively decomposable shaped product. The incorporation of an alkaline agent also has the effect of improving the storage stability of oxidizing agents such as hypochlorite. The alkaline agent is not particularly limited, but examples thereof include ammonia, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkali metal phosphates such as sodium phosphate, alkali metal carbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, carboxylates such as sodium lactate, potassium lactate, potassium hydrogen tartrate, sodium tartrate, sodium acetate, sodium malate, sodium gluconate, sodium fumarate, potassium gluconate, disodium succinate and trisodium citrate, and phosphates such as tetrasodium pyrophosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate and sodium dihydrogen phosphate. Sodium hydroxide, potassium hydroxide and calcium hydroxide are preferred in terms of odor, while sodium gluconate, trisodium citrate and tetrasodium pyrophosphate are preferred in terms of safety to the human body. When an alkaline agent is added, the amount added is preferably 0.001 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.1 to 5% by mass.

[0019] The incorporation of a chelating agent improves the decomposition rate of the oxidatively decomposable molded product by facilitating the dispersion and removal of dirt adhering to the surface of the oxidatively decomposable molded product and decomposition products generated by oxidative decomposition. Examples of chelating agents include, but are not limited to, ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, sodium metasilicate, sodium tripolyphosphate, citric acid or a salt thereof, glycolic acid, etc. When a chelating agent is incorporated, the amount is preferably 0.001 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 2% by mass.

[0020] By incorporating a thickener, the oxidizing agent can be retained on the surface of the oxidatively decomposable shaped product until decomposition is complete, even if the decomposition liquid is unlikely to remain on the surface of the oxidatively decomposable shaped product due to gravity, etc. The thickener is not particularly limited, but examples include organic thickeners such as carboxymethyl cellulose, guar gum, xanthan gum, alginic acid, pectin, polyvinyl alcohol, polyacrylic acid, polyvinylpyrrolidone, hyaluronic acid, carboxyvinyl polymer, carrageenan, and gum arabic, and mineral thickeners such as smectite, montmorillonite, attapulgite, and sepiolite.

[0021] The surface tension of the decomposition liquid of the present invention is preferably 15 to 60 mN / m, more preferably 20 to 30 mN / m. If the surface tension exceeds 60 mN / m, the decomposition rate of the oxidatively decomposable shaped product tends to be slow, while if the surface tension is less than 15 mN / m, handling of the decomposition liquid, such as measuring and transporting, tends to become difficult. Here, the surface tension can be measured by a method such as the ring method described in JIS-K2241.

[0022] The pH of the decomposition solution of the present invention is preferably 8 to 13, more preferably 8 to 11. When the pH is within the above range, the decomposition solution tends to have excellent decomposition properties and storage stability.

[0023] The viscosity of the decomposition liquid of the present invention is preferably 0.5 to 2000 mPa s, more preferably 0.5 to 50 mPa s. If the viscosity exceeds 2000 mPa s, the decomposition rate of the oxidatively decomposable shaped product tends to be slow, while if the viscosity is less than 0.5 mPa s, handling of the decomposition liquid, such as measuring and transporting, tends to become difficult. Here, the viscosity can be measured using a Brookfield viscometer under conditions of 20°C, a rotation speed of 60 rpm, and 60 seconds.

[0024] The water absorption of the oxidatively decomposable shaped product to be decomposed by the decomposition liquid of the present invention is preferably 0.01 to 30%, more preferably 0.01 to 3%. The water absorption can be measured by the weight change before and after 24 hours of water absorption as described in ASTM D-570.

[0025] <Oxidatively decomposable shaped product> The oxidatively decomposable shaped product is not particularly limited as long as it can be decomposed by an oxidizing agent. １ -NH-NH-A２ - (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.) It is preferable that the oxidatively decomposable shaped product contains a hydrazine structure represented by the following 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, and Z １ , Z ２ are each independently a divalent group containing a siloxane structure or a hydrocarbon group which may have a heteroatom. １ ~A ８ is a carbonyl group or a single bond, and A １ ~A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３ are each a reactive functional group independent of the other.) Examples of the oxidatively decomposable molded articles include those obtained by curing a hydrazine derivative represented by the following formula: The hydrazine derivative may be reacted alone or with a conventional monomer or polymer having another reactive functional group.

[0026] When an oxidatively decomposable shaped product has a hydrazine structure, gas bubbles such as nitrogen are generated during decomposition with an oxidizing agent and adhere to the surface of the shaped product, preventing contact with the oxidizing agent and slowing the decomposition rate. The decomposition liquid of the present invention can smoothly remove the gas bubbles, enabling the oxidatively decomposable shaped product to be decomposed in a short time.

[0027] In formula (2), n and m are both 0 or greater, but are each independently preferably 1 or greater, more preferably 2 or greater. When n is 1 or greater, the compound has two or more hydrazine structures (-A-NH-NH-A-), improving decomposition properties. There are no particular upper limits for n and m, but they can each be 50 or less.

[0028] 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 oxidatively decomposable molded product obtained by curing the hydrazine derivative has a three-dimensional crosslinked structure. The upper limit of k is not particularly limited, but can be 50 or less. Here, even if k is 0, Q １ or Q ２ When p1 is an acrylate, methacrylate, or primary amine, or when p1 or p2 is 2 or more, the oxidatively decomposable shaped article may have a three-dimensional crosslinked structure.

[0029] 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.

[0030] 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.

[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 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.

[0033] 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.

[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. 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.

[0036] 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.

[0037] 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 hetero atom. ２ is a divalent group containing a siloxane structure or a hydrocarbon group which may have a hetero atom.

[0038] In formula (2), Z１ 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] Z １ and Z ２ The structures of are independent of each other and may be the same or different. In addition, the hydrazine derivative represented by formula (2) may contain Z １ and Z ２ There may be multiple Z １ , Z ２ may be the same or different from each other. １ and Z ２When the structures of Z are different from each other, the decomposition property and solvent solubility of the oxidatively decomposable shaped product can be controlled by selecting a 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 １ Contains one or more Z ２ Contains two or more. １ Contains two or more 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.

[0048] The hydrazine derivative 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.

[0049] In formula (2), R １ , R ２ , R ３ , Z １ , Z ２It is preferable that at least one selected from the group consisting of is a group containing a siloxane structure. This is because it has the advantage of being able to impart properties such as sliding properties, releasability, antifouling properties, and chemical resistance to the oxidatively decomposable molded product, and 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.

[0050] In formula (2), R １ , R ２ , and R ３ and / or Z １ and Z ２ It is preferable that at least one selected from the group consisting of has a molecular weight of 200 or more. By adjusting the molecular weights of R and Z in this manner, the solubility of the oxidatively decomposable molded product in a solvent can be improved. Furthermore, when a cured product is produced using the hydrazine derivative, precipitation is suppressed, and molded products with uniform composition and physical properties can be obtained.

[0051] 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 Preferably, the molecular weight of the copolymer is 200 or more.

[0052] Similarly, Z １ and Z ２When 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.

[0053] The molecular weight is 200 or more, preferably 300 or more, 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 hydrazine derivative 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 an oxidatively decomposable shaped product with an oxidizing agent to obtain a decomposition product, followed by gel permeation chromatography (GPC), or by structural determination by NMR. When the molecular weight is determined by gel permeation chromatography (GPC), it is calculated as a weight average molecular weight (Mw).

[0054] In formula (2), it is preferable that n ≥ 1 and k ≥ 1. In this case, the hydrazine derivative is branched, enabling three-dimensional crosslinking.

[0055] In addition, in formula (2), n ≧ 1 and k ≧ 1, and Z １ The molecular weight of the hydrazine derivative 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.

[0056] In order to complicate the structure of the hydrazine derivative, 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.

[0057] 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

[0058] Examples of the reactive functional group include a hydroxyl group, an amino group, a thiol 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, a hydroxysilyl group, and an alkoxysilyl group.

[0059] p1, p2, and p3 are Q contained in the hydrazine derivatives. 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 ３ When 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.

[0060] 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).

[0061] 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, there is an advantage that the compound is easily decomposed with an oxidizing agent. When both are carbonyl groups, there is an advantage that the decomposition product is easily dissolved in a solution containing an oxidizing agent.

[0062] The weight average molecular weight of the hydrazine derivative is preferably 300 to 30000, more preferably 400 to 5000. When the molecular weight is within this range, it becomes easy to adjust the crosslink density and solvent solubility.

[0063] The hydrazine derivative is preferably liquid at 20 to 120° C., more preferably liquid at 30 to 60° C. In this case, it has excellent miscibility with other components when preparing the crosslinkable composition described below, and can prevent the other components from precipitating during molding.

[0064] <Method for Synthesizing Hydrazine Derivative> The method for synthesizing a hydrazine derivative is not particularly limited, and a hydrazine derivative in which carbonyl groups are present on both sides of —NH—NH— can be obtained by, for example, 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; reacting hydrazine with a carboxylic acid ester; reacting hydrazine with a carbonate compound; or reacting hydrazine with an isocyanate compound.

[0065] Furthermore, for example, a hydrazine derivative in which a carbonyl group is present on one side of —NH—NH— can be obtained by 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.

[0066] 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.

[0067] <Crosslinkable Composition> The crosslinkable composition is used to form, on a substrate, an oxidatively decomposable molded article that is decomposed upon contact with a solution containing 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.

[0068] (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 may be a crosslinking agent containing a hydrazine structure or an azo structure, and a crosslinking agent containing a hydrazine structure represented by the formula (1) is preferred, and an easily decomposable crosslinking agent represented by the formula (2) is more preferred. In the crosslinkable composition, the crosslinking agent containing a hydrazine structure may be used alone or in combination of two or more types.

[0069] (ii) In a crosslinkable composition in which a structure that is easily decomposable by an oxidizing agent is formed in the molecular chain by a crosslinking reaction, examples of components that form a structure that is easily decomposable by an oxidizing agent include 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.

[0070] The blending amounts of the non-reactive resin containing a hydrazine structure, the monofunctional curable resin containing a hydrazine structure, the crosslinking agent having a hydrazide group, and the crosslinking agent containing a hydrazine structure in the crosslinkable composition are preferably 1 to 99 wt %, more preferably 5 to 60 wt %, and even more preferably 10 to 45 wt %, of the total solid content. If the blending amount is less than 1 wt %, the chemical resistance of the oxidatively decomposable molded product tends to decrease, and if the blending amount exceeds 99 wt %, it tends to be difficult to form a uniform film.

[0071] The crosslinkable composition may contain a curable resin, a polymerization initiator, a solvent, a dye, a pigment, a surfactant, an ink fixing aid, and the like, in addition to the hydrazine derivative that functions as a crosslinking agent.

[0072] 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 the end, such as 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, a hydroxysilyl group, or an alkoxysilyl group.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] The curable resin is preferably one that is liquid at 40° C. or below, one that dissolves in a water-soluble organic solvent, or one that dissolves in an acid or alkaline aqueous solution. By using such a curable resin, the decomposition rate of the oxidatively decomposable molded product can be improved.

[0077] 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.

[0078] The polymerization initiator is not particularly limited as long as it is a compound that can catalyze the crosslinking reaction of the crosslinking agent or the curable resin, and either a thermal polymerization initiator or a photopolymerization initiator can be used. Examples of the polymerization initiator include radical generators such as alkylphenone compounds, benzoin compounds, benzophenone compounds, oxime ester compounds, and phosphine compounds; base generators such as oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzyl urethane compounds, and orthonitrobenzyl urethane compounds; 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 ethyl acetoacetate; zirconium compounds such as zirconium monoacetylacetate and zirconium tetraacetylacetate; amines such as triethylenediamine and 1,4-diazabicyclo[2,2,2]octane (DABCO); platinum compounds such as chloroplatinic acid and alkenylsiloxane platinum complexes; iron complexes; and cobalt complexes. The amount of the polymerization initiator in the composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the curable resin.

[0079] Examples of the solvent include water and organic solvents. Examples of the organic solvent include ether-based solvents, amine-based solvents, amide-based solvents, hydrocarbon-based solvents, alcohol-based solvents, ester-based solvents, aldehyde-based solvents, ketone-based solvents, and solvents containing carbon atoms, such as solvents containing carbon atoms and hetero atoms. Specific organic solvents are as described above. The blending amount of the solvent in the crosslinkable composition is preferably 5 to 99 wt %, more preferably 20 to 95 wt %.

[0080] The solvent 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 solvent 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, so the crosslinkable composition can be selected for a substrate with low heat resistance.

[0081] Examples of dyes include direct dyes, vat dyes, sulfur dyes, naphthol dyes, reactive dyes, acid dyes, acid mordant dyes, disperse dyes, cationic dyes, and fluorescent brighteners. From the viewpoint of dissolution rate in a solution containing an oxidizing agent, direct dyes, reactive dyes, acid dyes, and cationic dyes are preferred. Examples of chromophores include nitro-based, azo-based, stilbene-based, carbonium-based, quinoline-based, methine-based, thiazole-based, quinoneimine-based, anthraquinone-based, indigoid-based, and phthalocyanine-based dyes. Azo-based dyes are preferred because they can be decomposed in a solution containing an oxidizing agent. Furthermore, dyes preferably have functional groups such as sulfonic acid groups, carboxylic acid groups, amino groups, and hydroxyl groups. Such dyes are easily chemically adsorbed to the easily decomposable crosslinked layer containing a hydrazine structure and tend to have excellent solvent resistance and fastness. The amount of dye is preferably 0.1 to 50 wt % of the total solids content of the crosslinkable composition, and more preferably 1 to 20 wt %.

[0082] Examples of pigments include organic pigments such as nitro pigments, nitroso pigments, azo pigments, dye lake pigments, phthalocyanine pigments, threne pigments, quinacridone pigments, dioxazine pigments, and isoindolinone pigments; inorganic pigments such as oxide pigments, hydroxide pigments, sulfide pigments, selenide pigments, ferrocyanide pigments, chromate pigments, sulfate pigments, carbonate pigments, silicate pigments, phosphate pigments, carbon pigments, and metal powder pigments; mineral pigments; and natural pigments such as natural dye lake pigments. Preferred organic pigments include azo pigments that can be decomposed in a solution containing an oxidizing agent, and pigments having functional groups such as sulfonic acid groups, carboxylic acid groups, amino groups, and hydroxyl groups. Pigments with such functional groups tend to be chemically adsorbed to oxidatively decomposable molded products containing a hydrazine structure and are easily dispersed in a solution containing an oxidizing agent after the decomposition of the oxidatively decomposable molded products. Preferred inorganic pigments include carbon pigments and metal powder pigments that can be chemically adsorbed to oxidatively decomposable molded products containing a hydrazine structure. The average particle size of the pigment is preferably 0.005 to 1000 μm, more preferably 0.01 to 200 μm, and the amount of the pigment is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, of the total solid content of the crosslinkable composition.

[0083] Specific examples of the surfactant are as described above. The amount of the surfactant is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total solid content of the crosslinkable composition.

[0084] <Method for producing oxidatively decomposable molded product> The oxidatively decomposable molded product 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 a method of applying the crosslinkable composition to the substrate. Specific application 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, in-mold molding, and 3D printing. Another example of a method for laminating the crosslinkable composition is a method of laminating a film or sheet made of the crosslinkable composition to a substrate.

[0085] The crosslinking method of the crosslinkable composition includes light irradiation and heating. Specific crosslinking conditions are not particularly limited. When crosslinking is performed by light irradiation, the crosslinking conditions are 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 0.1 to 180 minutes, and more preferably 0.5 to 10 minutes.

[0086] It is preferable that at least a portion of the oxidatively decomposable shaped product is covered with paper, woven fabric, or nonwoven fabric. For example, the oxidatively decomposable composition is used as a primer or adhesive on paper or the like, and then coated on the paper or the like. When paper or the like and a film are bonded with the oxidatively decomposable composition, the decomposition liquid penetrates from the paper or the like into the adhesive layer, decomposing the adhesive layer, and the paper or the film can be recovered. The decomposition liquid of the present invention has low viscosity, so it can easily penetrate into paper or the like.

[0087] <Method for Decomposing Oxidatively Decomposable Molded Article> The method for decomposing an oxidatively decomposable molded article of the present invention is characterized by comprising a step of bringing the oxidatively decomposable molded article into contact with the decomposition liquid of the present invention.

[0088] The contact temperature when the oxidatively decomposable shaped product is brought into contact with the decomposition liquid of the present invention is preferably 100° C. or less, more preferably 15 to 50° C. The contact time is preferably 60 minutes or less, more preferably 10 minutes or less. If necessary, the product may be shaken or stirred during the reaction with the oxidizing agent.

[0089] The specific method for bringing the oxidatively decomposable shaped product into contact with the decomposition liquid of the present invention is not particularly limited, and examples thereof include a method of immersing the oxidatively decomposable shaped product in a solution containing an oxidizing agent, a method of spraying or dropping the solution containing an oxidizing agent onto the oxidatively decomposable shaped product, etc. Among these, a method of circulating the decomposition liquid within a system and a method of agitating the oxidatively decomposable shaped product are preferred in order to promote oxidative decomposition.

[0090] Another preferred method is to rub the surface of the oxidatively decomposable shaped product with fibers impregnated with a decomposition liquid. Rubbing the surface of the oxidatively decomposable shaped product quickly removes the decomposition products formed on the surface layer of the oxidatively decomposable shaped product, thereby accelerating oxidative decomposition. Examples of fibers to be impregnated with the oxidizing agent include paper, woven fabric, nonwoven fabric, and absorbent cotton. The fibers may be made of natural materials such as cellulose, fibroin, and keratin, or synthetic resins such as polypropylene, polyester, nylon, polylactic acid, polyethylene, polystyrene, polyurethane, polyvinyl alcohol, polyvinyl chloride, and polyacrylonitrile.

[0091] The oxidatively decomposable molded product is oxidized by contact with the decomposition liquid, and the decomposition products are 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.

[0092] After the step of contacting the oxidatively decomposable shaped product with the decomposition liquid of the present invention, fine solid components may be removed by centrifugation or filtration. Furthermore, solvent substitution, washing, etc. may also be performed. By undergoing these steps, the substrate of the oxidatively decomposable shaped product can also be recovered.

[0093] The oxidatively decomposable substance preferably produces water-soluble decomposition products upon reaction with an oxidizing agent. The water solubility of the decomposition products is preferably 1 g / L or more, more preferably 30 g / L or more. The water solubility is measured at 60°C at any one point in the pH range of 2 to 13. The decomposition products preferably have a melting point or softening point of 40°C or less, more preferably 20°C or less. By producing water-soluble decomposition products or decomposition products with a melting point or softening point of 20°C or less, the disassembly time of adhesive joints containing oxidatively decomposable substances is shortened. In the case of water-soluble decomposition products, the decomposition products are more likely to dissolve in a solution containing an oxidizing agent, which prevents the accumulation of decomposition products from inhibiting the reaction between the oxidizing agent and the oxidatively decomposable substance, and facilitates the penetration of the solution containing the oxidizing agent into the adhesive joint. Furthermore, the production of decomposition products with a melting point or softening point of 20°C or less is thought to cause a significant decrease in adhesive strength. However, the present invention is not limited to these mechanisms.

[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 mass" and "% by mass", respectively, unless otherwise specified.

[0095] Production Example 1 (Synthesis of Monomer A) 300 g of polyether polyol (Preminol P-5005, manufactured by AGC Inc.), 118 g of acetonitrile, and 46.8 g of triethylamine were mixed in a 1 L separable flask, and 43.4 g of di(N-succinimidyl) carbonate was added and stirred at 25°C for 2 hours. 24.8 g of 6-hydroxyhexane hydrazide was added and stirred at 25°C for 3 hours. After concentration under reduced pressure at 60°C, the mixture was dissolved in 340 g of ethyl acetate, and the organic layer was washed three times with 200 g of ion-exchanged water. The mixture was again concentrated under reduced pressure at 60°C and vacuum dried overnight at room temperature, yielding 303 g of Monomer A.

[0096] Production Example 2 (Preparation of Crosslinkable Composition) Monomer A synthesized in Production Example 1, monomer B (trimethylolpropane), and monomer C (hexamethylene diisocyanate) were blended in a mass ratio of 100:2:8, and then dibutyltin dilaurate was added as a catalyst in an amount of 0.5 mass% of the total solid content, followed by uniform mixing to prepare a crosslinkable composition.

[0097] Production Example 3 (Preparation of Oxidatively Decomposable Molded Product 1) 0.1 g of the crosslinkable composition prepared in Production Example 2 was molded into pellets with a diameter of 7 mm and heated at 70°C for 2 hours to prepare Oxidatively Decomposable Molded Product 1.

[0098] Production Example 4 (Production of Oxidatively Decomposable Molded Product 2) The crosslinkable composition produced in Production Example 2 was applied to a urethane film (TG88-1 (thickness 100 μm) manufactured by Takeda Sangyo Kaisha), a cloth (nylon woven fabric N2622PG (thickness 100 μm) manufactured by Shikisen Co., Ltd.) was placed so as to contact the coated surface, and then heated at 70° C. for 2 hours to produce an oxidatively decomposable molded product 2 with a film thickness of 1 mm between the urethane film and the nylon woven fabric. The urethane film and the nylon woven fabric were bonded together by the oxidatively decomposable molded product 2, and this laminate was cut into a size of 0.2 g and used for evaluation.

[0099] Production Example 5 (Synthesis of Monomer D) 72 g of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 kg of chloroform, 0.19 g of dibutyltin dilaurate, and 58 g of 1,3-bis(isocyanatomethyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a 2 L separable flask under ice cooling. After mixing, the mixture was returned to room temperature and stirred for 3 hours. The solvent was concentrated using an evaporator, and then 400 g of acetonitrile, 68 g of triethylamine, and 126 g of di(N-succinimidyl)carbonate were added and stirred at room temperature for 1 hour. 72 g of 6-hydroxyhexanoic acid hydrazide was then added and stirred at room temperature for an additional 2 hours. After distilling off the solvent using an evaporator, 600 ml of chloroform was added, and the organic solvent layer was washed three times with 400 g of ion-exchanged water, concentrated, and dried. The resulting viscous liquid was dissolved in 234 g of chloroform, and 15 g of triethylamine was added. Then, 10 g of acryloyl chloride was added dropwise to the solution while cooling with ice. After the addition, the mixture was returned to room temperature and stirred for 2 hours. The reaction solution was then washed three times with 600 g of ion-exchanged water, concentrated, and dried to obtain 58 g of Monomer D. The weight-average molecular weight measured by GPC was 4,500.

[0100] Production Example 6 (Preparation of Crosslinkable Composition) Monomer D synthesized in Production Example 5, Monomer E (4-acryloylmorpholine), and Monomer F (isobornyl acrylate) were blended in a mass ratio of 60:10:30, and then Omnirad TPO-N (manufactured by IGM Resins) was added as an initiator so that the amount was 9 mass % of the total solid content, and the mixture was mixed uniformly to prepare a crosslinkable composition.

[0101] Production Example 7 (Production of Oxidatively Decomposable Molded Product 3) The crosslinkable composition produced in Production Example 6 was applied to a PET film (Lumirror T60 (thickness 188 μm) manufactured by Toray Industries, Inc.) using a dispenser to form a circle with a diameter of 1.5 cm and a film thickness of 800 μm. ２ The molded product was irradiated with ultraviolet light of 1000 kJ / min for 2 minutes to prepare an oxidatively decomposable molded product 3.

[0102] <Water absorption rate> The water absorption rate of the oxidatively decomposable shaped articles 1 and 3 was measured based on the change in weight before and after 24 hours of water absorption in accordance with ASTM D-570. The water absorption rates of the oxidatively decomposable shaped articles 1 and 3 were 3% or less.

[0103] Examples 1 to 8 and Comparative Examples 1 to 2: Decomposition solutions were prepared by mixing the components according to the blending amounts shown in Table 1. The oxidizing agents used were a sodium hypochlorite aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., concentration 5%) and sodium dichloroisocyanurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The organic solvents used were an alcohol-based mixed solvent, Solmix AP-1 (manufactured by Japan Alcohol Sales Co., Ltd., ethanol 85.5% by mass, methanol 1.1% by mass, isopropanol 13.4% by mass), isopropanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Pure water was used as the diluent. The alkaline agent used was a sodium hydroxide aqueous solution (manufactured by Osaka Soda Co., Ltd.), diluted with pure water to a concentration of 1.5% by weight.

[0104]

[0105] <Evaluation of decomposition ability> The oxidatively decomposable shaped product 1 produced in Production Example 3 was immersed in the decomposition solutions produced in Examples 1 to 8 and Comparative Examples 1 and 2, and the state was visually observed every 30 minutes. In the decomposition solutions of Examples 1 to 5 and Example 8, the oxidatively decomposable shaped product 1 disappeared 30 minutes after the start. In the decomposition solution of Example 7, the oxidatively decomposable shaped product 1 disappeared 60 minutes after the start. In the decomposition solution of Example 6, the oxidatively decomposable shaped product 1 disappeared 90 minutes after the start. On the other hand, in the decomposition solutions of Comparative Examples 1 and 2, the oxidatively decomposable shaped product 1 remained even after 3 hours.

[0106] The oxidatively decomposable shaped product 2 produced in Production Example 4 was immersed in the decomposition solutions produced in Examples 1 to 8 and Comparative Examples 1 and 2, and the state was visually observed every 15 minutes. In the decomposition solutions of Examples 1 to 8, the layered state of the oxidatively decomposable shaped product 2 was disintegrated 15 minutes after the start of the immersion. On the other hand, in the decomposition solutions of Comparative Examples 1 and 2, the layered state of the oxidatively decomposable shaped product 2 was maintained even after 30 minutes.

[0107] Examples 9-15 and Comparative Examples 3-4: Decomposition solutions were prepared by mixing the components according to the blending amounts shown in Table 2. The oxidizing agents used were sodium dichloroisocyanurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sodium hypochlorite pentahydrate (manufactured by Nippon Light Metal Co., Ltd., SHC5), and calcium hypochlorite (manufactured by Tosoh Corporation, PTG3). The organic solvents used were ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), isosorbide dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), dipropylene glycol dimethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and polyethylene glycol (PEG200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The diluent used was pure water. The alkaline agents used were trisodium citrate dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and tetrasodium pyrophosphate decahydrate (manufactured by Kanto Chemical Co., Inc.).

[0108]

[0109] <Evaluation of decomposition ability> The surface of the oxidatively decomposable molded product 3 produced in Production Example 7 was rubbed with nonwoven fabrics impregnated with the decomposition liquids produced in Examples 9 to 15 and Comparative Examples 3 and 4, and the condition was visually observed every 3 minutes. When the decomposition liquids of Examples 11 to 14 were used, the oxidatively decomposable molded product 3 had disappeared 3 minutes after the start of friction. When the decomposition liquids of Examples 9 and 15 were used, the oxidatively decomposable molded product 3 had disappeared 6 minutes after the start of friction. When the decomposition liquid of Example 10 was used, the oxidatively decomposable molded product 3 had disappeared 9 minutes after the start of friction. On the other hand, when the decomposition liquids of Comparative Examples 3 and 4 were used, the oxidatively decomposable molded product 3 remained even 12 minutes after the start of friction.

Claims

1. A decomposition liquid for decomposing oxidatively decomposable molded articles, comprising an organic solvent, an oxidizing agent, and water.

2. The oxidatively decomposable molded product is represented by the 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 The decomposition liquid according to claim 1, which is an oxidatively decomposable shaped product containing a hydrazine structure represented by the following formula:

3. The decomposition liquid according to claim 1 or 2, wherein the oxidatively decomposable shaped product has a three-dimensional crosslinked structure.

4. The oxidatively decomposable molded product is represented by the following 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, and Z １ , Z ２ are each independently a divalent or higher valent group containing a siloxane structure, or a hydrocarbon group which may have a heteroatom. １ ~A ８ is a carbonyl group or a single bond, and A １ ~A ８ At least one of the groups is a carbonyl group. １ , Q ２ , Q ３ The decomposition liquid according to claim 2 or 3, which is an oxidatively decomposable molded product obtained by curing a hydrazine derivative represented by the following formula:

5. The decomposition liquid according to any one of claims 1 to 4, wherein the oxidizing agent is hypochlorous acid, hypochlorite, isocyanuric acid chloride, hydrogen peroxide, or ozone.

6. The decomposition liquid according to any one of claims 1 to 5, wherein the concentration of the oxidizing agent is 0.001 to 3 mass %.

7. The decomposition liquid according to any one of claims 1 to 6 or 2, wherein the organic solvent is an alcohol, an amine, or an ether.

8. The decomposition solution according to any one of claims 1 to 7, further comprising an alkaline agent.

9. The decomposition liquid according to any one of claims 1 to 8, further comprising a surfactant.

10. The decomposition liquid according to any one of claims 1 to 9, wherein at least a portion of the oxidatively decomposable shaped article is covered with paper, woven fabric or nonwoven fabric.

11. A method for decomposing oxidatively decomposable molded products, comprising the step of contacting the oxidatively decomposable molded products with the decomposition liquid according to any one of claims 1 to 10.

12. The method for decomposing oxidatively decomposable molded products according to claim 11, wherein the decomposition liquid is circulated within the system in the contacting step.

13. The method for decomposing oxidatively decomposable molded products according to claim 11 or 12, wherein the oxidatively decomposable molded products are agitated in the contacting step.

14. A method for decomposing oxidatively decomposable molded products according to claim 11 or 12, wherein in the contacting step, the surface of the oxidatively decomposable molded product is rubbed with fibers impregnated with the decomposition liquid.

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