S硬化性組成物、硬化物、及び、物品

Abstract

Provided are: a curable composition in which (poly)rotaxane and an epoxy resin can be crosslinked under a relatively mild condition; a novel (poly)rotaxane suitable for said curable composition and a method for producing the same; and a cured substance and an article having excellent toughness and a composition having excellent storage stability, which can be obtained using the curable composition. The curable composition contains: (poly)rotaxane that includes a cyclic molecule having an ethylenically unsaturated bond; an epoxy compound; and a curing agent. The (poly)rotaxane includes a cyclic molecule having at least one group selected from a group represented by formula (1) and a group represented by formula (2). The reference symbols in formula (1) and formula (2) are as defined in the specification.

Description

[Technical field]

[0001] The present invention relates to a (poly)rotaxane and a method for producing the same, a curable composition, a cured product, an article, and a composition. [Background technology]

[0002] Polyrotaxane, a complex having a structure in which linear molecules are threaded through cyclic molecules, has properties different from conventional polymer materials and various applications are being considered. For example, a cured product formed by cross-linking cyclic molecules contained in polyrotaxane has mechanical properties different from those of cured products of conventional curable resins.

[0003] Patent Document 1 discloses a photocrosslinkable composition comprising a photocrosslinkable polyrotaxane having cyclic molecules having specific photopolymerizable groups. Patent Document 2 discloses a crosslinkable composition containing a compound having two or more oxirane groups and / or oxetane groups, and a rotaxane having a cyclic molecule having a specific functional group capable of reacting with the compound. Patent Document 3 discloses an epoxy resin composition containing an epoxy resin, a specific polyrotaxane, and a curing agent that reacts with the epoxy resin. In Patent Document 3, the curing agent is an epoxy resin curing agent, and crosslinks epoxy resins together in a composition containing the polyrotaxane. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2011 / 105532 [Patent Document 2] International Publication No. 2014 / 196636 [Patent Document 3] International Publication No. 2015 / 129513 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a curable composition capable of crosslinking a (poly)rotaxane and an epoxy resin under relatively mild conditions, a novel (poly)rotaxane suitable for the curable composition and a production method thereof, a cured product and article having excellent toughness obtained by using the curable composition, and a composition having excellent storage stability. [Means for solving the problem]

[0006] The (poly)rotaxane according to the present invention comprises a cyclic molecule having one or more groups selected from a group represented by the following formula (1) and a group represented by the following formula (2).

[0007] [ka] however, R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, X 1 is a linking group or a single bond connecting to a ring structure, * indicates the end of the ring structure.

[0008] One embodiment of the (poly)rotaxane is 1 is represented by the following formula (X).

[0009] [ka] however, X 2 is *-OR 21-**, *-OC(=O)-R 21 -**, *-C(=O)-OR 21 -**, *-NH-C(=O)-R 21 -**, *-C(=O)-NH-R 21 -**, *-NH-C(=O)-OR 21 -**, *-OC(=O)-NH-R 21 -** stands for X 2 If there are multiple, there are multiple X 2 may be the same or different, R 21 is a hydrocarbon group which may have a substituent, and R 21 If there are multiple, there are multiple R 21 may be the same or different, L is *-O-**, *-OC(=O)-**, *-C(=O)-O-**, *-NH-C(=O)-**, *-C(=O)-NH-**, *-NH-C(=O)-O-**, *-OC(=O)-NH-**, m is an integer from 1 to 200; n is 0 or 1, * denotes the end of the ring structure, ** denotes R 3 The lateral ends are shown.

[0010] In one embodiment of the (poly)rotaxane, L is *-OC(=O)-**.

[0011] The method for producing a (poly)rotaxane according to the present invention is a method for producing the (poly)rotaxane, comprising the steps of: A step of preparing a (poly)rotaxane (1A) having a cyclic molecule having a functional group selected from a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group; The method includes a step of reacting a functional group of the (poly)rotaxane (1A) with one or more compounds selected from the following formula (1a) and the following formula (2a).

[0012] [ka] however, R1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)- or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)- or -NH-C(=O)-O- in the carbon chain, X 3 is a group having a functional group selected from a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.

[0013] The curable composition according to the present invention contains a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, an epoxy compound (B), and a curing agent (C).

[0014] In one embodiment of the curable composition, the epoxy compound (B) includes a polyfunctional epoxy compound.

[0015] In one embodiment of the curable composition, the curing agent (C) includes one or more selected from polyfunctional amines and polyfunctional thiols.

[0016] In one embodiment of the curable composition, the cyclic molecule having an ethylenically unsaturated bond is a cyclic molecule having one or more groups selected from the group represented by formula (1) and the group represented by formula (2).

[0017] One embodiment of the curable composition is 1 is represented by the above formula (X). In one embodiment of the curable composition, L is *-OC(=O)-**.

[0018] The present invention provides a cured product of the above curable composition. The present invention provides an article comprising the above-mentioned cured product. The present invention also provides a composition containing a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, and an epoxy compound (B). Effect of the Invention

[0019] The present invention provides a curable composition capable of crosslinking a (poly)rotaxane and an epoxy resin under relatively mild conditions, a novel (poly)rotaxane suitable for the curable composition and a production method thereof, a cured product and article obtained by using the curable composition, and a composition having excellent storage stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The (poly)rotaxane and its production method, curable composition, cured product, article, and composition according to the present invention will be described below. In the present invention, the term "(poly)rotaxane" is a general term for rotaxane and polyrotaxane. In the present invention, the term "(meth)acrylate" is a general term for acrylate and methacrylate, and (meth)acrylic acid and the like are equivalent thereto. In this specification, the group represented by formula (1) may be simply referred to as "group (1)." The same applies to other substituents, chemical formulas, etc. In the present invention, a cyclic molecule refers to a molecule having a ring structure through which a linear molecule can penetrate. In addition, in the present invention, a cyclic structure refers to the portion of a cyclic molecule excluding groups (1), (2), and (3). In this specification, the term "to" indicating a range of values ​​includes the lower and upper limits, unless otherwise specified. In this specification, the solid content in a composition refers to the components constituting the composition excluding the solvent.

[0021] [Curable composition] The curable composition according to the present invention (hereinafter, may be referred to as the present curable composition) contains a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, an epoxy compound (B), and a curing agent (C).

[0022] The present curable composition uses, as the curing agent (C), a curing agent capable of reacting with both the ethylenically unsaturated bond of the (poly)rotaxane (A) and the epoxy group of the epoxy compound (B). The present curable composition can crosslink the (poly)rotaxane (A) and the epoxy compound (B) via the curing agent (C). The present curable composition can be cured under relatively mild heating conditions by selecting the curing agent (C). On the other hand, in a state in which the curing agent (C) is not blended, the reactivity between the (poly)rotaxane (A) and the epoxy compound (B) is poor, and therefore the composition according to the present invention described below has excellent storage stability as a preliminary preparation of the present curable composition.

[0023] The present curable composition may contain at least a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, an epoxy compound (B), and a curing agent (C), and may further contain other components within the scope of the effects of the present invention. Each component of such a curable composition will now be described in detail.

[0024] <(Poly)rotaxane (A)> In the present invention, a (poly)rotaxane is a complex in which a linear molecule penetrates a cyclic molecule and the linear molecule has blocking groups on both sides of the cyclic molecule. The blocking groups prevent the cyclic molecule from being detached from the linear molecule. The cyclic molecule can move in the linear direction of the linear molecule, with the area between the blocking groups as the movable area. The (poly)rotaxane (A) in the present curable composition comprises a cyclic molecule having an ethylenically unsaturated bond. In the present composition, the ethylenically unsaturated bond is crosslinked with the epoxy compound (B) via the curing agent (C). The cyclic molecule remains relatively mobile with respect to the linear molecule even after crosslinking. Therefore, when the cured product of the present curable composition is subjected to an external force, the (poly)rotaxane flexibly deforms, and the force acting on the entire cured product is alleviated. For this reason, the cured product obtained from the present curable composition has excellent toughness and impact resistance.

[0025] (cyclic molecule) In the (poly)rotaxane (A), the cyclic molecule has a ring structure through which a linear molecule described later can penetrate, and an ethylenically unsaturated bond. The ethylenically unsaturated bond may have any structure as long as it can be crosslinked with the curing agent (C) described below. Examples of the ethylenically unsaturated bond include a (meth)acryloyl group, a vinyl group, and an allyl group.

[0026] In the (poly)rotaxane (A), the substituent having an ethylenically unsaturated bond is preferably a group represented by the following formula (3).

[0027] [ka] however, R 11 is a group having an ethylenically unsaturated bond, X 11 is a linking group or a single bond that links to a ring structure, * indicates the end of the ring structure.

[0028] From the viewpoints of ease of synthesis and toughness of the cured product, R 11 is preferably a group represented by the following (11) to (16).

[0029] [ka] however, R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, p is 0 or 1; * denotes X in group (3). 11 The lateral ends are shown.

[0030] R 1 , R 2 , R 4 and R 5 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1 ~R 5 The alkyl group in the formula (I) may be a linear or branched alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. When the alkyl group has 2 or more carbon atoms, it may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain. For example, when the alkyl group has the above bond in the carbon chain, R 1 ~R 5 The alkyl group in the formula (I) can be represented as *-R'-QR" (wherein R' and R" are each independently an alkyl group having 1 or more carbon atoms, the sum of the number of carbon atoms in R' and the number of carbon atoms in R" is 2 to 12, and Q is -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O-). Examples of the substituent that the alkyl group may have include a halogen atom and a phenyl group.

[0031] R 1 , R 2 , R 4 and R 5 From the standpoint of ease of synthesis and molecular stability, each of them independently represents preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have the above-mentioned Q in the carbon chain, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms not having Q, and further preferably a hydrogen atom or a methyl group. Also, R 3From the standpoint of ease of synthesis and molecular stability, is preferably an alkyl group having 1 to 6 carbon atoms which may have the above-mentioned Q in the carbon chain, more preferably an alkyl group having 1 to 6 carbon atoms not having Q, and further preferably a methyl group or an ethyl group.

[0032] When p is 0, the group (15) is *-CH2=CH2, and when p is 1, the group (15) is *-O-CH2=CH2.

[0033] In group (3), R 11 Among these, the group (11) or the group (12) is preferred from the standpoint of ease of synthesis and toughness of the cured product.

[0034] X 11 is a linking group or a single bond that connects to a ring structure. X 11 When is a single bond, group (3) is *-R 11 It is. X 11 When is a linking group, it is preferably a linking group represented by the following formula (X1).

[0035] [ka] however, X 12 is *-OR 12 -**, *-OC(=O)-R 12 -**, *-C(=O)-OR 12 -**, *-NH-C(=O)-R 12 -**, *-C(=O)-NH-R 12 -**, *-NH-C(=O)-OR 12 -**, *-OC(=O)-NH-R 12 -** stands for X 12 If there are multiple, there are multiple X 12 may be the same or different, R 12 is a hydrocarbon group which may have a substituent, and R 12 If there are multiple, there are multiple R 12 may be the same or different, L 11are *-O-**, *-OC(=O)-**, *-C(=O)-O-**, *-NH-C(=O)-**, *-C(=O)-NH-**, *-NH-C(=O)-O-**, *-OC(=O)-NH-**, m1 is an integer from 1 to 200, n1 is 0 or 1, * denotes the end of the ring structure, ** denotes R in group (3). 11 The lateral ends are shown.

[0036] R 12 Examples of the hydrocarbon group in the formula include a linear alkylene group, a branched alkylene group, a cycloalkylene group, an arylene group, and a group consisting of a combination thereof. The straight-chain alkylene group preferably has a carbon number of 1 to 12, more preferably has a carbon number of 1 to 8, and still more preferably has a carbon number of 1 to 6. Examples of the straight-chain alkylene group include a methylene group, an ethylene group, a propylene group, and a hexylene group. The branched alkylene group is preferably a structure having an alkyl group as a substituent of the linear alkylene group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group. The cycloalkylene group may be a monocyclic or condensed ring having 5 to 12 carbon atoms, and a cyclopentylene group or a cyclohexylene group is preferred. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group. Examples of groups formed by these combinations include a group in which a methylene group is connected to a phenylene group. 12 Examples of the substituent that may be contained in the alkyl group include a halogen atom and an alkoxy group having 1 to 6 carbon atoms.

[0037] L 11 and n1 is X 12 and R 11 represents the connection of 12 and R 11 The compound is appropriately selected based on the ease of synthesis depending on the structure of R. 11When R is group (13), group (15) (p=1), or group (16), n1 is preferably 0. 11 When is a group (11), a group (12), a group (14) or a group (15) (p=0), n1 may be either 0 or 1. Among these, n1 is preferably 1 from the viewpoint of ease of synthesis. In addition, from the viewpoint of ease of synthesis, L 11 is preferably *-OC(=O)-**.

[0038] When m1 is 2 or more, the linking group (X1) can be considered as a polymer. 12 may be the same homopolymer, X 12 When the linking group (X1) is a copolymer, the bonding order is not particularly limited, and the copolymer may be any of a random copolymer, a block copolymer, and an alternating copolymer. From the standpoint of toughness of the resulting cured product, m is from 1 to 200, preferably from 1 to 100, and more preferably from 1 to 40.

[0039] When the linking group (X1) is regarded as a polymer, specific examples of the polymer include polyether, polyester, polyamide, polyurethane, etc. In the (poly)rotaxane (A), the linking group (X1) is preferably a polyether, polyester, polyamide, or a copolymer thereof from the viewpoints of ease of synthesis and chemical stability. The polyester structure can be suitably synthesized, for example, by ring-opening polymerization of lactone. Examples of the lactone include ε-caprolactone, δ-valerolactone, and γ-butyrolactone. The polyamide structure can be suitably synthesized, for example, by ring-opening polymerization of lactam. Examples of the lactam include ε-lactam, δ-lactam, and γ-lactam. These can be used alone or in combination of two or more.

[0040] In the present curable composition, the cyclic molecule constituting the (poly)rotaxane is preferably one or more groups selected from the group represented by the following formula (1) and the group represented by the following formula (2), among the groups (3), in terms of excellent chemical stability.

[0041] [ka] however, R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, X 1 is a linking group or a single bond connecting to a ring structure, * indicates the end of the ring structure.

[0042] R in group (1) and group (2) 1 ~R 3 R in the groups (11) and (12) 1 ~R 3 The same applies to the preferred embodiments. X 1 represents X in the group (3). 11 The same applies to the preferred embodiments.

[0043] The ring structure constituting the cyclic molecule may be appropriately selected from those capable of including the linear molecule described below. Specific examples of the ring structure include cyclodextrin, crown ether, cyclophane, calixarene, etc., and from the viewpoint of ease of introducing a substituent, cyclodextrin, cyclophane, and calixarene are preferred, and cyclodextrin is more preferred. Examples of cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. When the ring structure is cyclodextrin, it is preferable that the ring structure includes a structure in which the group (3) is introduced into the hydroxyl group of the cyclodextrin.

[0044] The number of groups (3) per cyclic molecule is not particularly limited and may be appropriately adjusted within the range of, for example, 1 to 24, taking into consideration factors such as the toughness of the resulting cured product. For example, when the ring structure is α-cyclodextrin, the number of groups (3) per cyclic molecule is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8, from the standpoint of toughness of the resulting cured product. When the ring structure is β-cyclodextrin, the number of groups (3) per cyclic molecule is preferably 1 to 15, more preferably 1 to 12, and even more preferably 1 to 10, from the standpoint of toughness of the resulting cured product. When the ring structure is γ-cyclodextrin, the number of groups (3) per cyclic molecule is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 12, from the standpoint of toughness of the resulting cured product. In the case of a polyrotaxane having a plurality of cyclic molecules, some of the cyclic molecules may not have the group (3).

[0045] The cyclic molecule may have a substituent different from the above group (3) within the scope of the effect of the present invention. Examples of such a substituent include a group represented by the following formula (4). Formula (4) *-X 11 -R 21 however, X 11is a linking group or a single bond that links to a ring structure, R 21 are hydroxyl, carboxyl, amino and isocyanate groups, * indicates the end of the ring structure.

[0046] In addition, X 11 is the same as that in the group (3), and preferred embodiments are also the same. However, n1 in the formula (X1) is preferably 0. The number of groups (4) per cyclic molecule is not particularly limited, but may be, for example, 0 to 23. Specifically, when the ring structure is α-cyclodextrin, the number of groups (4) per cyclic molecule is preferably 0 to 17. When the ring structure is β-cyclodextrin, the number of groups (4) per cyclic molecule is preferably 0 to 20. When the ring structure is γ-cyclodextrin, the number of groups (4) per cyclic molecule is preferably 0 to 23.

[0047] In the present invention, the (poly)rotaxane may have at least one cyclic molecule. From the viewpoint of toughness of the obtained cured product, it is preferable that the (poly)rotaxane has two or more cyclic molecules, that is, it is a polyrotaxane. Furthermore, the number of cyclic molecules is preferably 2 to 250, more preferably 3 to 200, and even more preferably 4 to 150.

[0048] The number of ethylenically unsaturated bonds per cyclic molecule is not particularly limited, but is preferably 1 to 24 from the viewpoint of the toughness of the obtained cured product. For example, when the ring structure is α-cyclodextrin, the number of ethylenically unsaturated bonds per cyclic molecule is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8 from the viewpoint of the toughness of the obtained cured product. When the ring structure is β-cyclodextrin, the number of ethylenically unsaturated bonds per cyclic molecule is preferably 1 to 15, more preferably 1 to 12, and even more preferably 1 to 10 from the viewpoint of the toughness of the obtained cured product. Also, when the ring structure is γ-cyclodextrin, the number of ethylenically unsaturated bonds per cyclic molecule is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 12 from the viewpoint of the toughness of the obtained cured product. In the case of a polyrotaxane having a plurality of cyclic molecules, some of the cyclic molecules may not have an ethylenically unsaturated bond.

[0049] (linear molecule) The linear molecule has a linear structure that passes through the ring structure of the cyclic molecule, and a blocking group that inhibits the cyclic molecule from being released. The linear structure may be a linear polymer, etc. In the present invention, the linear structure may have a branched structure as long as the movement of the cyclic molecules is not hindered. Specific examples of the linear polymer include vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, and vinyl chloride-vinyl acetate copolymers; acrylic polymers such as poly(meth)acrylic acid, poly(meth)acrylamide, polymethyl(meth)acrylate, and acrylonitrile-methyl acrylate copolymers; cellulose polymers such as carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; polyethers such as polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacetal; Examples of the polyolefins include polyolefins such as olefins and polypropylene; polyamides such as nylon; polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and other polystyrenes; polysiloxanes such as polydimethylsiloxane; polydienes such as polyisoprene and polybutadiene; polyesters, polyamines, polyimides, polyanilines, polyurethanes, polycarbonates, polyethyleneimines, casein, gelatin, starch; polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof. From the standpoint of the stability of the linear molecule and the toughness of the cured product, the linear structure is preferably polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, or polyvinyl methyl ether, more preferably polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, or polypropylene, and among these, polyethylene glycol is even more preferable.

[0050] The blocking group may be appropriately selected from substituents that are bulkier than the opening of the cyclic molecule. Specific examples of the blocking group include aryl groups such as phenyl, naphthyl, and pyrenyl; alkyl groups having an aryl group as a substituent, such as trityl; cyclic alkyl groups such as adamantyl; known compounds having a condensed ring, such as fluoresceins and steroids, and cyclodextrins. These blocking groups may further have a substituent. Examples of the substituent include alkyl groups, oxyalkyl groups, hydroxy groups, cyano groups, sulfonyl groups, carboxy groups, amino groups, aryl groups, and halogen atoms. In the (poly)rotaxane (A), from the viewpoint of molecular stability and the like, the blocking group is preferably a dinitrophenyl group, an adamantyl group, a trityl group, a pyrenyl group, a fluorescein, or a cyclodextrin, and more preferably an adamantyl group or a trityl group. In addition, the blocking groups present in the linear molecule may be the same or different, but from the viewpoint of ease of synthesis, it is preferable that the blocking groups are the same substituents.

[0051] The molecular weight of the linear molecule may be appropriately adjusted depending on the number of cyclic molecules contained in the (poly)rotaxane (A), the range of motion required for the cyclic molecules, etc. The molecular weight of the linear molecule may be adjusted, for example, in the range of 1,000 to 1,000,000, preferably 2,000 to 500,000, more preferably 3,000 to 200,000.

[0052] The number of ethylenically unsaturated bonds per (poly)rotaxane may be appropriately adjusted according to the molecular weight of the linear molecule, the number of cyclic molecules, the physical properties required for the cured product, and the like. When the cyclic molecule is a compound derived from cyclodextrin, the modification rate (= number of ethylenically unsaturated bonds / number of reactive hydroxyl groups (hydroxyl value) of the raw material (poly)rotaxane × 100 [%]) can be adjusted as a guide. The number of reactive hydroxyl groups of the raw material (poly)rotaxane is the number of reactive hydroxyl groups of the (poly)rotaxane before the ethylenically unsaturated bonds are introduced, and is given as a hydroxyl value mgKOH / g that is known in the art. For example, the commercially available product, Selm Super Polymer SH1300P from Advanced Soft Materials Co., Ltd., has a hydroxyl value of 85 mgKOH / g and has 1.52 mmol of reactive hydroxyl groups per 1 g of the polyrotaxane. The above modification rate can be calculated as an average value using NMR. In the present (poly)rotaxane, the average modification rate is preferably from 1 to 99%, more preferably from 1 to 80%, and further preferably from 1 to 70%.

[0053] The (poly)rotaxane (A) may be synthesized, for example, by the method described below or the method described in International Publication No. 2011 / 105532, or may be a commercially available product, such as the Selm Super Polymer SM / SA series from Advanced Soft Materials Co., Ltd.

[0054] <Epoxy compound (B)> In the present curable composition, the epoxy compound (B) may be appropriately selected depending on the physical properties required for the resulting cured product. The epoxy compound (B) may have one or more epoxy groups in one molecule, and from the viewpoint of three-dimensional crosslinking, a polyfunctional epoxy compound having two or more epoxy groups is preferred. Among them, the polyfunctional epoxy compound preferably has 2 to 50 epoxy groups, more preferably 2 to 20 epoxy groups. The epoxy compound (B) may be a low molecular weight compound or a high molecular weight compound. The epoxy group may be a structure having an oxirane ring structure, and may be, for example, a glycidyl group, an epoxycyclohexyl group, or the like. Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol S type epoxy resins, diphenyl ether type epoxy resins, hydroquinone type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, fluorene type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, trifunctional type epoxy resins, tetraphenylolethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol A nucleus-containing polyol type epoxy resins, polypropylene glycol type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic type epoxy resins, heterocyclic type epoxy resins, and polymers containing a monomer containing an epoxy group such as glycidyl (meth)acrylate. These can be used alone or in combination of two or more.

[0055] <Hardening agent (C)> In the present curable composition, the curing agent (C) is appropriately selected from those having a substituent capable of crosslinking with both the (poly)rotaxane (A) and the epoxy compound (B). As such a substituent, an amino group or a sulfanyl group (thiol) is preferable. As the curing agent (C), from the viewpoints of reactivity and toughness of the obtained cured product, a polyfunctional amine having two or more amino groups in one molecule or a polyfunctional thiol having two or more sulfanyl groups in one molecule is preferred, and among these, a polyfunctional thiol is preferred.

[0056] The amine in the polyfunctional amine is preferably a primary amine or a secondary amine. Examples of the polyfunctional amine include ethylenediamine, hexamethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 2-butyl-2-ethyl-1,5-pentanediamine, and diethylene glycol bis(diaminophenyl)amine. (3-aminopropyl)ether, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-diaminocyclohexane, 2,2'-oxybis(ethyleneamine), 2,2'-(ethylenedioxy)bis(ethylamine), 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diamino-2-hydroxypropane, 2,2'-ethylenedianiline, 4,4'-ethylenedianiline, 3,3'-methylene Dianiline, 4,4'-methylenedianiline, 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 4,4'-diaminostilbene, 4,4'-oxydianiline, 4,4'-thiodianiline, 4'',4''''-(hexafluoroisopropylidene)-bis-(4-phenylaniline), 2,3-diaminophenol, 4'-aminobenzo-15-crown-5, 2,4-dimethoxyaniline, 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenebis(2,6-diethylaniline) , 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-diaminooctafluorobiphenyl, 1,2-phenylenediamine, 2,3-diaminotoluene, 3,4-diaminotoluene, 3,3'-diaminobenzidine, 4-chloro-1,2-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine, 1,2,4,5-benzenetetramine, 4,5-dichloro-1,2-phenylenediamine, 1,3-phenylenediamine, 2,6-diaminotoluene, 2,4-Diaminotoluene, 2,4,6-trimethyl-1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 2,4-diaminophenol, 4-(2-hydroxyethylthio)-1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-diaminotoluene, 2,5-dimethyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 1,2 -Diphenylethylenediamine, 1,2-bis(4-methoxyphenyl)ethylenediamine, metaxylenediamine, paraxylenediamine, α,ω-diaminopolyethylene glycol, α,ω-diaminopolypropylene glycol, α,ω-diaminopolydimethylsiloxane, polyallylamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diisopropylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-diisopropyl -1,3-propanediamine, N,N'-dimethyl-1,6-hexanediamine, N,N'-bis(3,3-dimethylbutyl)-1,2-cyclohexanediamine, 1,3-cyclohexanebis(methylamine), N,N'-diethyl-2-butylene-1,4-diamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,3-bis[tris(hydroxymethyl)methylamino]propane, 4,4'-bipiperidine, 4,4'-ethylenebipiperidine, 4,4'-trimethylenebipiperidine, piperazine, 2,6-dimethylpiperazine, 2 ,5-Dimethylpiperazine, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclopentadecane, sparteine, 1,4,10,13-tetraxa-7,16-diazacyclooctadecane, 1,2-dianilinoethane, N,N'-diphenyl-1,4-phenylenediamine, N,N'-diphenylbenzidine, 3,3'-(hexafluoroisopropylidene)dianiline, 4,4'-(hexafluoroisopropylidene)dianiline, 2,Examples of the diaminonaphthalene include 3-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,1'-binaphthyl-2,2'-diamine, 2,7-diaminofurene, and N,N'-dibenzylethylenediamine. These may be used alone or in combination of two or more.

[0057] Examples of polyfunctional thiols include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, 1,4-butanediol dithioglycolate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakisthiolate, glycolate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), and other esters of various polyhydric alcohols with thiol group-containing carboxylic acids such as thioglycolic acid and mercaptopropionic acid, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like. These may be used alone or in combination of two or more. Moreover, a polyfunctional amine and a polyfunctional thiol may be used in combination.

[0058] <Other ingredients> The present curable composition may further contain other components within the range in which the effects of the present invention are exhibited, such as a solvent, a surfactant, a plasticizer, a surface lubricant, a leveling agent, a softener, an antioxidant, an antiaging agent, a light stabilizer, an ultraviolet absorber, a curing accelerator, and an inorganic or organic filler.

[0059] The solvent can be appropriately selected from solvents capable of dissolving or dispersing the (poly)rotaxane (A), the epoxy compound (B), and the curing agent (C). Examples of the solvent include water, esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, isopropanol and butanol; cyclic ethers such as tetrahydrofuran (THF) and dioxane; nitriles such as acetonitrile and propionitrile; halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane, and mixed solvents thereof. Among these, water, esters, ketones, or aromatic hydrocarbons are preferred.

[0060] The curable composition may contain a curing accelerator for accelerating the curing reaction. Examples of the curing accelerator include known tertiary amines, acid anhydrides, phosphorus compounds, etc. In addition, when a polyfunctional amine is used as the curing agent (C), the polyfunctional amine itself may also function as the curing accelerator.

[0061] The filler may be appropriately selected from known fillers, and is not particularly limited. Suitable examples of the filler include insulating fillers such as aluminum hydroxide, aluminum oxide, aluminum nitride, magnesium hydroxide, magnesium oxide, talc, and boron nitride, and conductive fillers such as gold, silver, copper, nickel, aluminum, carbon, and graphite. A cured product of a curable composition containing a filler has excellent flexural modulus, etc. On the other hand, a cured product of a curable composition not containing a filler has excellent impact strength, so the use of a filler may be appropriately selected depending on the application of the cured product, etc.

[0062] In the present curable composition, the content of the (poly)rotaxane (A) is preferably from 0.01 to 80 mass%, more preferably from 0.05 to 40 mass%, and even more preferably from 0.1 to 15 mass%, based on the solid content constituting the present curable composition, from the viewpoints of toughness of the obtained cured product and the like. In the present curable composition, the content of the epoxy compound (B) is preferably 3 to 95 mass%, more preferably 5 to 95 mass%, and even more preferably 10 to 85 mass%, based on the solid content constituting the present curable composition, from the viewpoints of toughness of the obtained cured product and the like. In the present curable composition, the content of the curing agent (C) is preferably from 0.01 to 95 mass%, more preferably from 0.1 to 90 mass%, and even more preferably from 1 to 85 mass%, based on the solid content constituting the present curable composition, from the viewpoints of toughness of the obtained cured product and the like. When a filler is used in the present curable composition, the content of the filler is preferably from 0.01 to 90 mass%, more preferably from 0.1 to 80 mass%, and even more preferably from 1 to 70 mass%, based on the solid content constituting the present curable composition, from the viewpoints of toughness of the obtained cured product and the like.

[0063] The present curable composition can be suitably used in the same applications as known thermosetting compositions, etc. Suitable applications include, for example, paints, adhesives, molding materials, modeling materials, resin modifiers, laminating materials, sealing materials, electrical insulating materials, electrical and electronic component materials, reinforcing agents, vibration-proofing, vibration-damping and vibration-isolating materials, scratch-resistant films, coating agents, binders, optical materials, rubber modifiers, fibers, mechanical and automotive materials, building materials, clothing and sporting goods, etc. The curable composition undergoes a sufficient crosslinking reaction, for example, by heating at room temperature (25° C.) to 90° C., preferably at 40° C. to 80° C., for 5 minutes to 10 hours, preferably for 30 minutes to 4 hours. As the composition cures under such relatively mild conditions, it can be suitably used for substrates with low heat resistance.

[0064] [Cured materials and articles] The cured product according to the present invention is obtained by thermally curing the curable composition. Also, the article according to the present invention comprises the cured product as at least a part thereof. The cured product according to the present invention is a cured product of the curable composition, and therefore has excellent toughness. The method for producing the cured product and article is not particularly limited, and examples thereof include a method in which the product is molded by a known molding method or printing method depending on the desired shape, etc., and then heated under the above-mentioned conditions.

[0065] [Composition] The composition according to the present invention (hereinafter also referred to as the present composition) contains a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, and an epoxy compound (B). This composition does not contain a curing agent (C) and has poor reactivity between the (poly)rotaxane (A) and the epoxy compound (B), and therefore has excellent storage stability. Since the present curable composition can react at a relatively low temperature, for example, by preparing a curing agent (C) separately from the present composition and mixing the present composition with the curing agent (C) immediately before use, the crosslinking reaction during storage can be suppressed, and the composition can be used stably. Each component constituting the present composition is similar to that of the present curable composition, and therefore description thereof will be omitted here.

[0066] [(Poly)rotaxane] The (poly)rotaxane according to the present invention (hereinafter also referred to as the present (poly)rotaxane) comprises a cyclic molecule having one or more groups selected from a group represented by the following formula (1) and a group represented by the following formula (2):

[0067] [ka] however, R 1 and R 2each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, X 1 is a linking group or a single bond connecting to a ring structure, * indicates the end of the ring structure.

[0068] The (poly)rotaxane has excellent chemical stability and is therefore suitable for use in the curable composition. In addition, the (poly)rotaxane can be combined with a photoinitiator and, if necessary, other photocurable monomers to prepare a photocurable composition, since the ethylenically unsaturated bond of the (poly)rotaxane can function as a photopolymerizable group. The aspects of the present (poly)rotaxane are the same as those explained in the curable composition, and the preferred aspects are also the same, so the explanation here is omitted.

[0069] <Method of manufacturing the (poly)rotaxane> The method for producing the present (poly)rotaxane is not particularly limited, but the following production method is preferred from the viewpoint of ease of synthesis. That is, the production method for the (poly)rotaxane according to the present invention (hereinafter also referred to as the present production method) is as follows: A step of preparing a (poly)rotaxane (1A) having a cyclic molecule having a functional group selected from a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group; The method includes a step of reacting a functional group of the (poly)rotaxane (1A) with one or more compounds selected from the following formula (1a) and the following formula (2a).

[0070] [ka] however, R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)- or -NH-C(=O)-O- in the carbon chain, R 3 represents a hydrogen atom or an alkyl group which may have a substituent and which may have -O-, -S-, -C(=O)-, -OC(=O)-, -NH-C(=O)- or -NH-C(=O)-O- in the carbon chain, X 3 is a group having a functional group selected from a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.

[0071] (Preparation of (Poly)rotaxane (1A)) The (poly)rotaxane (1A) may be produced by referring to, for example, International Publication No. 2005 / 080469, International Publication No. 2005 / 108464, International Publication No. 2009 / 136618, etc., or a commercially available product may be used. Examples of commercially available products include the Selm Super Polymer SH series from Advanced Soft Materials Co., Ltd. The Selm Super Polymer SH series polyrotaxanes are complexes in which the linear molecule has a polyethylene glycol chain and an adamantyl group, and the cyclic molecule has a caprolactone chain grafted to α-cyclodextrin either directly or via a hydroxypropyl group, and the end of the caprolactone chain is a hydroxyl group.

[0072] When the ring structure used in the polyrotaxane is cyclodextrin, compound (1a) or compound (2a) may be directly introduced into a hydroxyl group of the cyclodextrin. The group (4) may be introduced into the hydroxyl group. When the ring structure is cyclodextrin, cyclophane, calixarene, or a crown ether having an aromatic ring, a hydroxyl group, a carboxyl group, an amino group, or an isocyanate group may be introduced into the aromatic ring.

[0073] (Reaction of Functional Groups of (Poly)rotaxane (1A) with Compound (1a) and Compound (2a)) The (poly)rotaxane (1A) is mixed with one or more compounds selected from the compound (1a) and the compound (2a), and the mixture is heated as necessary, whereby the group (1) or group (2) can be introduced into the (poly)rotaxane (1A).

[0074] R in compound (1a) and compound (2a) 1 ~R 3 The preferred embodiments of X are the same as those in the formula (1) and formula (2). 3 In this case, a substituent having reactivity with the cyclic molecule to be introduced may be appropriately selected. Of the compounds (1a), the compound represented by the following formula (1b) is preferable. Also, of the compounds (2a), the compound represented by the following formula (2b) is preferable.

[0075] [ka] However, R 3 is the same as in formula (1a) and formula (2a).

[0076] Compound (1b) and compound (2b) can be prepared, for example, by reacting maleic acid, maleic anhydride, or fumaric acid with R 3 It can be obtained by reacting with -OH to form a monoester. EXAMPLES

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Synthesis Examples 1 to 4 are examples for synthesizing polyrotaxanes according to the present invention.

[0078] (Production Example 1: Synthesis of monoethyl maleate) 10 g of maleic anhydride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 ml of absolute ethanol in a flask at room temperature, and then 15.5 ml of triethylamine was added dropwise while cooling with ice and stirring. After stirring the pale yellow reaction solution at room temperature overnight, excess ethanol was removed under reduced pressure using an evaporator, and the resulting residue was diluted with 50 ml of ethyl acetate and washed with 0.5N hydrochloric acid. The aqueous layer was extracted twice with 25 ml of ethyl acetate, and the combined organic layer was washed with 25 ml of 0.5N hydrochloric acid and then with 25 ml of saturated saline. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 10.2 g of the target monoethyl maleate as a pale yellow oily liquid.

[0079] (Synthesis Example 1: Synthesis of Polyrotaxane) Under a nitrogen atmosphere, 1.0 g of SH1300P (caprolactone graft polyrotaxane: Advanced Soft Materials Co., Ltd.) was dissolved in 4.0 ml of chloroform in a three-neck flask, and 2.0 ml of a chloroform solution containing 219 mg of monoethyl maleate (1 equivalent to the hydroxyl value of SH1300P) and 260 mg of diisopropylcarbodiimide was added dropwise with a syringe. The reaction solution was heated at 60°C, heated and stirred overnight, purified, and dried to obtain 0.89 g of maleic acid-modified polyrotaxane (polyrotaxane having group (1)) of Synthesis Example 1 as a white solid. The modification rate calculated from the NMR spectrum was 9.6%.

[0080] (Synthesis Example 2: Synthesis of Polyrotaxane) Under a nitrogen atmosphere, 120 g of SH1300P (caprolactone graft polyrotaxane: Advanced Soft Materials Co., Ltd.) was dissolved in 480 ml of THF dehydrated overnight with 4 Å molecular sieves containing 8.68 g of monoethyl maleate (0.33 equivalents relative to the hydroxyl value of SH1300P) in a three-neck flask, and 12.8 ml of diisopropyl azodicarboxylate and then 13.7 ml of n-tributylphosphine (0.3 equivalents relative to the hydroxyl value of SH1300P) were added dropwise to the mixture at -15°C using a syringe pump while maintaining the internal temperature at -15°C or lower. The reaction mixture was stirred at -15°C for one hour, then stirred in an ice bath, and then heated to room temperature and stirred overnight. The mixture was purified and dried to obtain 120.8 g of maleic acid modified polyrotaxane (polyrotaxane having group (1)) of Synthesis Example 2 as a white solid. The modification rate calculated from the NMR spectrum was 26.3%.

[0081] (Synthesis Example 3: Synthesis of polyrotaxane) Under a nitrogen atmosphere, 10 g of SH1300P (caprolactone graft polyrotaxane: Advanced Soft Materials Co., Ltd.) was dissolved in 40 ml of THF dehydrated overnight with 4 Å molecular sieves containing 0.72 g of monoethyl fumarate (0.33 equivalents relative to the hydroxyl value of SH1300P, purchased from Tokyo Chemical Industry Co., Ltd.) in a three-neck flask, and 1.06 ml of diisopropyl azodicarboxylate and then 1.14 ml of n-tributylphosphine (0.3 equivalents relative to the hydroxyl value of SH1300P) were added dropwise with a syringe pump at -15°C while maintaining the internal temperature at -15°C or lower. The reaction mixture was stirred at -15°C for one hour, then stirred in an ice bath, and then warmed to room temperature and stirred overnight. The mixture was purified and dried to obtain 9.8 g of maleic acid modified polyrotaxane (polyrotaxane having group (1)) of Synthesis Example 3 as a white solid. The modification rate calculated from the NMR spectrum was 27.3%.

[0082] (Synthesis Example 4: Synthesis of Polyrotaxane) Under a nitrogen atmosphere, 1.0 g of SH1300P (caprolactone grafted polyrotaxane: Advanced Soft Materials Co., Ltd.) was dissolved in 4.0 ml of chloroform in a two-neck flask, and 2.0 ml of a chloroform solution containing 219 mg of monoethyl fumarate (1 equivalent to the hydroxyl value of SH1300P, purchased from Tokyo Chemical Industry Co., Ltd.) and 260 mg of diisopropylcarbodiimide was added dropwise with a syringe. The reaction solution was heated at 60°C, heated and stirred overnight, purified, and dried to obtain 1.0 g of fumaric acid-modified polyrotaxane (polyrotaxane having group (2)) of Synthesis Example 4 as a white solid. The modification rate calculated from the NMR spectrum was 16.9%.

[0083] <Preparation of Curable Composition and Production of Cured Product> The following Examples 2 to 3, Examples 5 to 7, and Example 9 are working examples, and Examples 1, 4, and 8 are comparative examples.

[0084] (Example 1) 25 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 15 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) were mixed, and 37.5 mg of tetramethylethylenediamine was added thereto and further mixed to obtain a curable composition 1. The above curable composition 1 was heated in a Teflon (registered trademark) mold at room temperature for 1 hour and then at 70° C. for 1 hour to obtain a cured product 1.

[0085] (Example 2) 27.5 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq), 2.3 g of the maleic acid ester-modified polyrotaxane of Synthesis Example 1, and 16.5 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) were mixed, and 41.2 mg of tetramethylethylenediamine was added thereto and further mixed to obtain a curable composition 2. The above curable composition 2 was heated in a Teflon mold at room temperature for 1 hour and then at 70° C. for 1 hour to obtain a cured product 2.

[0086] (Example 3) 27.5 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq), 4.9 g of the maleic acid ester-modified polyrotaxane synthesized in Synthesis Example 1, and 16.5 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) were mixed, 41.2 mg of tetramethylethylenediamine was added thereto, and the mixture was further mixed to obtain curable composition 3. The above curable composition 3 was heated in a Teflon mold at room temperature for 1 hour and then at 70° C. for 1 hour to obtain a cured product 3.

[0087] (Example 4) 20 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent weight 187 g / eq) and 12 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) were mixed, and 32 g of aluminum hydroxide (filler: CW-308 manufactured by Sumitomo Chemical Co., Ltd., particle size 45 μm) and 60 mg of triethylamine (purchased from Tokyo Chemical Industry Co., Ltd.) were added thereto, and the mixture was further mixed. The mixture was degassed under reduced pressure with an oil pump to obtain a curable composition 4. The above curable composition 4 was heated in a Teflon mold at room temperature for 1 hour, then at 60° C. for 1 hour, and at 80° C. for 1 hour to obtain a cured product 4.

[0088] (Example 5) 20 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 0.32 g of the maleic acid ester modified polyrotaxane of Synthesis Example 1 were mixed thoroughly in advance, and 12 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) and 32 g of aluminum hydroxide (CW-308: 45 μm manufactured by Sumitomo Chemical Co., Ltd.) were added and mixed. 60 mg of triethylamine (purchased from Tokyo Chemical Industry Co., Ltd.) was added and further mixed. The mixture was degassed under reduced pressure with an oil pump to obtain a curable composition 5. The above curable composition 5 was heated in a Teflon mold at room temperature for 1 hour, then at 60° C. for 1 hour, and at 80° C. for 1 hour to obtain a cured product 5.

[0089] (Example 6) 20 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 1.68 g of the maleic acid ester modified polyrotaxane of Synthesis Example 1 were mixed thoroughly in advance, and 12 g of pentaerythritol tetrakis(3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) and 32 g of aluminum hydroxide (CW-308: 45 μm manufactured by Sumitomo Chemical Co., Ltd.) were added and mixed. 60 mg of triethylamine (purchased from Tokyo Chemical Industry Co., Ltd.) was added and further mixed. The mixture was degassed under reduced pressure with an oil pump to obtain a curable composition 6. The above curable composition 6 was heated in a Teflon mold at room temperature for 1 hour, then at 60° C. for 1 hour, and at 80° C. for 1 hour to obtain a cured product 6.

[0090] (Example 7) 20 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 0.646 g of SA1305P_20 (caprolactone grafted acrylic group modified polyrotaxane: manufactured by Advanced Soft Materials Co., Ltd.) were mixed thoroughly in advance, and the ethyl acetate dissolving the polyrotaxane was removed under reduced pressure, and 12 g of pentaerythritol tetrakis (3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) and 32 g of aluminum hydroxide (CW-308: 45 μm manufactured by Sumitomo Chemical Co., Ltd.) were added and mixed. 60 mg of triethylamine (purchased from Tokyo Chemical Industry Co., Ltd.) was added and further mixed. The mixture was degassed under reduced pressure with an oil pump to obtain a curable composition 7. The above curable composition 7 was heated in a Teflon mold at room temperature for 1 hour, then at 60° C. for 1 hour, and at 80° C. for 1 hour to obtain a cured product 7.

[0091] (Example 8) 20 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 0323 g of SH1300P (caprolactone graft polyrotaxane having no ethylenically unsaturated bond: manufactured by Advanced Soft Materials Co., Ltd.) were dissolved in 0.6 ml of dichloromethane and mixed thoroughly in advance, and the dichloromethane in which the polyrotaxane was dissolved was removed under reduced pressure, and 12 g of pentaerythritol tetrakis (3-mercaptopropionate) (PEMP-LV manufactured by SC Organic Chemical Co., Ltd.) and 32 g of aluminum hydroxide (CW-308: 45 μm manufactured by Sumitomo Chemical Co., Ltd.) were added and mixed. 60 mg of triethylamine (purchased from Tokyo Chemical Industry Co., Ltd.) was added and further mixed. The mixture was degassed under reduced pressure with an oil pump to obtain a curable composition 8. The above curable composition 8 was heated in a Teflon mold at room temperature for 1 hour, then at 60° C. for 1 hour, and then at 80° C. for 1 hour to obtain a cured product 8.

[0092] (Example 9) 2.9 g of bisphenol A type epoxy resin (EPICLON850-S manufactured by DIC Corporation, epoxy equivalent 187 g / eq) and 0.18 g of the maleic acid ester-modified polyrotaxane synthesized in Example 1 were thoroughly mixed in advance, and 0.5 g of N,N'-bis(3-aminopropyl)ethylenediamine (purchased from Tokyo Chemical Industry Co., Ltd.) was added thereto and mixed to obtain curable composition 9. It was confirmed that the above curable composition 9 could be cured by heating at 60° C. for 0.5 hour and then at 80° C. for 0.5 hour.

[0093] The compositions of the curable compositions are shown in Table 1. [Table 1]

[0094] <Evaluation> The cured products of Examples 1 to 8 were ground to prepare test pieces of 80 mm x 10 mm x 4 mm. Next, a bending test was performed with reference to JIS K 7171 (three-point bending test) to measure the bending modulus, bending strength, and stress-strain curve. In addition, an impact test was performed with reference to JIS K 7111-1 (Charpy impact test) with respect to the same test pieces to measure the impact strength. The test conditions were as follows: The area under the strain curve refers to the value obtained by integrating the area of ​​the stress-strain curve of Examples 1 to 8 over the section up to breakage. The area under the strain curve ratio refers to the ratio of the areas under the strain curve of cured products 2 and 3 to the area under the strain curve of cured product 1, which is set to 100%, for cured products 1 to 3 that do not contain a filler, and the area under the strain curve of cured products 4 to 8, which contains a filler, to the area under the strain curve of cured product 4, which is set to 100%, for cured products 5 to 8, which are similarly expressed as a ratio. The larger the area under the strain curve, the more excellent the toughness can be evaluated. The results are shown in Table 2. (Bending test) Test piece: 80mm x 10mm x 4mmt Test speed: 2mm / min Distance between fulcrums: 64mm Temperature: 23℃ Equipment: Universal material testing machine Model 5966 (Instron) (Impact test) Test piece: 80mm x 10mm x 4mmt Lifting angle: 150 degrees Test direction: Edgewise Nominal pendulum energy: 1J Temperature: 23℃ Equipment: Digital impact testing machine DG-UB type (manufactured by Toyo Seiki Co., Ltd.)

[0095] [Table 2]

[0096] The cured materials 1 to 3 which do not contain a filler and the cured materials 4 to 8 which contain a filler will be considered separately. Cured products 1 to 3 that do not contain a filler tend to have excellent impact strength. In particular, it was revealed that cured products 2 and 3 containing polyrotaxanes having cyclic molecules with ethylenically unsaturated bonds have further improved impact strength while suppressing the decrease in the area under the strain curve. In this way, it was revealed that the cured product obtained using the present curable composition that contains (poly)rotaxane (A) having cyclic molecules with ethylenically unsaturated bonds, epoxy compound (B), and curing agent (C) and does not contain a filler has high toughness and is resistant to impact. In addition, the cured products 4 to 8 containing a filler tend to have a high flexural modulus. In particular, it was revealed that the cured products 4 to 7 containing polyrotaxanes having cyclic molecules with ethylenically unsaturated bonds have an increased area under the strain curve. In this way, it was revealed that the cured product obtained by using the present curable composition containing (poly)rotaxane (A) having cyclic molecules with ethylenically unsaturated bonds, epoxy compound (B), curing agent (C), and filler is overall strong against loads that cause distortion. As described above, the curable composition according to the present invention, which contains the (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond, the epoxy compound (B), and the curing agent (C), can be It was revealed that the (poly)rotaxane (A) and the epoxy compound (B) crosslink via the curing agent (C), and the toughness and impact resistance of the resulting cured product are improved.

[0097] This application claims priority based on Japanese Patent Application No. 2020-009147, filed on January 23, 2020, the disclosure of which is incorporated herein in its entirety.

Claims

1. A method for producing a polymerizable composition comprising: a (poly)rotaxane (A) having a cyclic molecule having an ethylenically unsaturated bond; an epoxy compound (B); and a curing agent (C); The cyclic molecule having an ethylenically unsaturated bond is a cyclic molecule having one or more groups selected from a group represented by the following formula (1) and a group represented by the following formula (2), The curable composition, wherein the curing agent (C) comprises a polyfunctional thiol. 【Chemistry 1】 however, R １ and R ２ is a hydrogen atom, R ３ represents an alkyl group having 1 to 6 carbon atoms which does not have -O-, -S-, -C(=O)-, -O-C(=O)-, -NH-C(=O)-, or -NH-C(=O)-O- in the carbon chain, X １ is a linking group linked to a ring structure represented by the following formula (X), In formula (1) and formula (2), * indicates a terminal of the ring structure, 【Chemistry 2】 however, X ２ is *-O-C(=O)-R ２１ - represents **, and X ２ If there are multiple, there are multiple X ２ may be the same or different, R ２１ is a linear alkylene group having 1 to 6 carbon atoms, R ２１ If there are multiple R ２１ may be the same or different, L is *-O-C(=O)-**, m is an integer from 1 to 200; n is 1, In L, * is the terminal of the ring structure, ** is R ３ The lateral ends are shown.

2. The curable composition of claim 1 , wherein the epoxy compound (B) comprises a multifunctional epoxy compound.

3. A cured product of the curable composition according to claim 1 or 2.

4. An article comprising the cured product according to claim 3.

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