Hardened product, shape memory member, ligature, suture, and wearable device

Abstract

To provide a cured product that can achieve both of a low driving temperature and a large deformation rate.SOLUTION: A crystalline cured product comprises a cured composition containing a curable compound 1 represented by the formula (1) and a curable compound 2 represented by the formula (2).SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates to a cured product, a shape-memory member, a ligature, a suture, and a wearable device. [Background technology]

[0002] Aliphatic polyester resins such as polycaprolactone are known to have excellent biodegradability, and research into them is ongoing. Non-Patent Document 1 describes a temperature-responsive poly(ε-caprolactone) membrane. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Journal of Controlled Release,2006,vol.110,p408-413 Summary of the Invention [Problem to be solved by the invention]

[0004] The film described in Non-Patent Document 1 had a shape memory ability, that is, it memorized the deformation applied and returned to the shape before the deformation was applied when heated to a certain temperature (hereinafter, this temperature is also referred to as the "driving temperature"). However, there was room for improvement in the amount of deformation that could be memorized (hereinafter, also referred to as the "deformation rate").

[0005] Therefore, an object of the present invention is to provide a cured product that can achieve both a low operating temperature and a large deformation rate. Another object of the present invention is to provide a shape-memory member, a ligature, a suture, and a wearable device. [Means for solving the problem]

[0006] As a result of extensive investigations aimed at achieving the above object, the present inventors have found that the above object can be achieved by the following configuration.

[0007] [1] A crystalline cured product obtained by curing a composition containing a curable compound 1 represented by the following formula 1 described below and a curable compound 2 represented by the following formula 2 described below. [2] The cured product according to [1], wherein a molar ratio of the content of the curable compound 2 to the total content of the curable compound 1 and the curable compound 2 is 0.01 to 0.65. [3] The cured product according to [1] or [2], wherein the total number of repeating units of an oxyalkylenecarbonyl group, a repeating unit derived from D-lactic acid, and a repeating unit derived from L-lactic acid in the polymer chain of the curable compound 2 is 10 to 100. [4] The cured product according to any one of [1] to [3], wherein the curable compound 1 is represented by formula 1B described below. [5] The cured product according to [4], wherein the curable compound 2 is represented by formula 1C described below. [6] The cured product according to any one of [1] to [5], wherein a test specimen prepared by the following method does not have crystallinity. (Method of preparing the test specimen: 500 mg of the above-mentioned curable compound 2, 15 mg of benzoyl peroxide, and 695 μL of xylene are mixed to obtain a composition, which is then heated to 80°C to polymerize. The resulting polymer is washed with acetone, shrunk in methanol, and then dried under reduced pressure to obtain a test specimen.) [7] The cured product according to any one of [1] to [5], wherein the curable compound 1 is represented by formula 1D described below. [8] The cured product according to [7], wherein the hydrocarbon group in formula 1D is at least one group selected from the group consisting of -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2C(CH3)2CH2-. [9] The cured product according to [7] or [8], wherein the curable compound 2 is represented by formula 1E described below.

[10] The cured product according to [2], wherein the ratio is 0.15 to 0.60.

[11] The cured product according to

[10] , wherein the ratio is 0.15 to 0.40.

[12] The cured product according to

[10] , wherein the ratio is 0.40 to 0.55.

[13] The cured product according to any one of [1] to

[12] , having a crystallinity of 10.0 to 24.0%.

[14] The cured product according to

[13] , having a crystallinity of 15.0 to 20.0%.

[15] The cured product according to any one of [1] to

[14] , which has a crystalline melting peak temperature of 36.0 to 42.0 as measured by a differential scanning calorimeter.

[16] A shape-memory member comprising the cured product according to any one of [1] to

[15] .

[17] A ligature device comprising the shape memory member described in

[16] .

[18] A suture comprising the shape memory member described in

[16] .

[19] A wearable device comprising the shape memory member described in

[16] . Effect of the Invention

[0008] According to the present invention, it is possible to provide a cured product that can achieve both a low operating temperature and a large deformation rate. Another object of the present invention is to provide a shape-memory member, a ligature, a suture, and a wearable device. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic plan view of an example of an embodiment of a ligature tool of the present invention. [Diagram 2] FIG. [Diagram 3] This is a schematic front view of a ligature device that has been spread out, heated to the softening point of the hardened material (a temperature close to the melting point), and then cooled to fix the temporary shape, and then wrapped around the biological part to be ligated. [Figure 4] 1 is a schematic front view showing a state in which a biological part is ligated by the ligature tool that has returned to its temporary shape. FIG. [Diagram 5] This is an image showing the temporary suture applied to an incision on the back of a Sprague-Dawley rat. [Figure 6]This image shows that when the back of an SD rat was warmed by spraying 37°C hot water onto it, the suture contracted (returned to its permanent shape) and the incision was closed. [Figure 7] 1 is an example of an embodiment of a wearable device of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0011] (Definition of terms) In this specification, the permanent shape refers to a state in which internal (residual) stress is relaxed, in other words, the most thermodynamically stable shape, and typically refers to the shape obtained when a cured material is heated to near (or above) the melting temperature of the crystal without the application of external stress, and then cooled to room temperature. The melting temperature of the crystals means the peak top temperature of the endothermic peak during the temperature rise process when the cured product is subjected to differential scanning calorimetry (when there are multiple endothermic peaks, the peak top temperature of the highest temperature peak is used). The vicinity of the melting temperature means about the end temperature on the high temperature side of the endothermic peak in differential scanning calorimetry. The differential scanning calorimetry of the cured product is performed by the method described in the examples below.

[0012] In this specification, the term "temporary shape" refers to a shape obtained when a material is deformed by applying an external stress, heated to near the melting temperature of the crystals, and then cooled to about the crystallization temperature (or lower), in which the deformation is temporarily fixed by crystallization, etc. The crystallization temperature refers to the temperature at the top of the exothermic peak during the cooling process when differential scanning calorimetry is performed on the cured material.

[0013] [Cured product] The cured product according to the embodiment of the present invention is a crystalline cured product obtained by curing a composition containing a curable compound 1 represented by formula 1 described below and a curable compound 2 represented by formula 2 described below.

[0014] The mechanism by which the above-mentioned cured product provides the effects of the present invention is not entirely clear, but the present inventors speculate as follows: Note that the mechanism described below is merely speculation, and even if the problem of the present invention is solved by a mechanism other than the following mechanism, the member having the above configuration is included in the scope of the present invention.

[0015] The shape memory ability of a cured material is achieved by reheating the material, which has a temporary shape fixed by the melting and reforming of the crystals, causing the crystals to melt again and the stretched polymer chains between the crosslinks to return to their original state, thereby recreating the permanent shape.

[0016] The melting temperature of the crystals in the hardened material is the temperature (driving temperature) that triggers the shape transition. If the hardened material is applied to a living body and body temperature (surface temperature or internal temperature of the body) is intended to be the driving temperature, it is necessary to naturally lower the melting temperature (melting point) of the crystals.

[0017] Conventionally, it has been believed that an effective way to lower the melting point is to shorten the molecular chain between crosslink points of the cured product. Based on the above findings, in Cited Document 1, a composition containing a difunctional terminal poly(ε-caprolactone) macromonomer and a tetrafunctional terminal poly(ε-caprolactone) macromonomer is cured, and the melting temperature of the crystals of the obtained cured product is successfully reduced to about 42-3°C.

[0018] However, according to the investigations of the present inventors, it has been found that, although the melting point can be lowered by shortening the molecular chain between crosslinking points, it is difficult to obtain a cured product having a larger deformation ratio. On the other hand, the inventors have also found that simply lengthening the molecular chain between crosslinking points in an attempt to improve the deformation rate increases the crystallinity of the cured product, and the melting temperature of the crystals, i.e., the operating temperature, increases. In other words, there is a trade-off between lowering the operating temperature and improving the deformation ratio, and it is difficult to achieve both.

[0019] The present inventors have been working on the development of a shape-memory member having a better deformation ratio than conventional ones while maintaining the melting point of the cured product at the body temperature. As a result, it has been found that if a curable compound 2 containing in its structure a molecular chain consisting of a copolymer having all of a repeating unit derived from D-lactic acid (hereinafter also referred to as "D-lactic acid unit"), a repeating unit derived from L-lactic acid (hereinafter also referred to as "L-lactic acid unit"), and a repeating unit represented by formula 3 (hereinafter also referred to as "unit 3") described below is used, a crystalline structure is unlikely to be formed even if the molecular chain between the crosslinking points is long, so that a cured product having an excellent deformation ratio while maintaining a low melting point can be obtained, and the present invention has been completed. The components contained in this cured product will be described in detail below.

[0020] The cured product according to an embodiment of the present invention (hereinafter also referred to as the "cured product") is a crystalline cured product obtained by curing a composition containing a curable compound 1 represented by formula 1 described below and a curable compound 2 represented by formula 2 described below. In addition, the term "crystalline" means that a melting peak is detected when DSC (differential scanning calorimetry) is measured (heating rate 5°C / min) by the method described in the Examples below.

[0021] The crystal melting peak temperature is not particularly limited, but is preferably 31.0 to 48.0°C. In particular, when the cured product is used as a wearable device, suture, or the like and is driven by contacting the body surface, the peak melting temperature is preferably 31.0 to 35.0°C, more preferably 32.0 to 34.5°C, taking into account the body surface temperature. On the other hand, when the cured product is placed or placed in a living body as a ligature or the like and actuated, the peak melting temperature is preferably 35.0 to 43.0°C, taking into consideration the temperature inside the body, and more preferably exceeds 35.0°C and is not higher than 42.0°C.

[0022] The crystallinity of the cured product is not particularly limited, but the crystallinity measured by a differential scanning calorimeter is preferably 10.0 to 24.0%. When the cured product is operated on the surface of a living body, the crystallinity is preferably 10.0 to 15.0%, and when the cured product is operated inside a living body, the crystallinity is preferably 15.0 to 24.0%, more preferably 15.0 to 20.0%, and further preferably the lower limit is more than 15.0%.

[0023] [Composition] The method for obtaining the cured product is not particularly limited, but the cured product can be obtained by applying energy (typically, heating) to a composition containing the curable compound 1 and the curable compound 2 described below, and other components as necessary, to cure the composition. Each component contained in the composition used to produce the cured product will be described in detail below.

[0024] <Curable compound 1> The composition used to produce the cured product (hereinafter, also simply referred to as "composition") contains a curable compound 1 represented by the following formula 1. The content of the curable compound 1 in the composition is not particularly limited, but in relation to the curable compound 2 described later, when the total is taken as 100 mol %, the content is preferably 20 mol % or more, more preferably 30 mol % or more, even more preferably 35 mol % or more, and particularly preferably 40 mol % or more. The upper limit is preferably 99 mol % or less, more preferably 95 mol % or less, further preferably 90 mol % or less, and particularly preferably 85 mol % or less.

[0025] In particular, when the cured product is to be actuated on the surface of a living body, the content of the curable composition 1 is preferably 45 to 60 mol %. When the cured product is driven in a living body, the content of the curable composition 1 is preferably 60 to 99 mol %, and more preferably 60 to 85 mol %.

[0026] [ka]

[0027] In formula 1, L 1 represents a poly(oxyalkylenecarbonyl) group, and X 1 represents a group having a curable group, R 1 represents a hydrogen atom or the above-mentioned monovalent substituent not having a curable group, q1 represents an integer of 2 or more, p1 represents an integer of 0 or more, and when q1 is 2 and p1 is 0, M 1 represents a single bond or a divalent group, and when q1 is 2 and p1 is 1 or more, and when q1 is 3 or more, M 1 represents a p1+q1 valent group, and multiple R 1 , and L 1 may be the same or different.

[0028] L in Equation 1 1 The poly(oxyalkylenecarbonyl) group is a divalent group consisting of a polymer chain having oxyalkylenecarbonyl groups as repeating units, and specifically, is a group represented by the following formula II.

[0029] [ka]

[0030] In formula II, L 21 represents an alkylene group, L 21 The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 20, and more preferably 2 to 10. Among these, L is preferred because it provides a member having the excellent effect of the present invention. 21 As the alkylene group, an alkylene group having 2 to 10 carbon atoms is more preferable.

[0031] In addition, in the formula II, n represents a number of 2 or more, and is not particularly limited, but is preferably 2 to 200, more preferably 2 to 100, further preferably 5 to 50, and particularly preferably 10 to 30.

[0032] As described later, the curable compound 1 can also be prepared by ring-opening polymerization of a cyclic ester. In this case, the number n can be adjusted by the charging ratio of a ring-opening polymerization initiator (e.g., a polyhydric alcohol) and a monomer (e.g., a lactone compound). More specifically, the lactone compound is charged so that the desired number n of reactions occur with one hydroxy group of the polyhydric alcohol.

[0033] The above number n is the 1 It can be determined by H-NMR (Nuclear Magnetic Resonance) measurement.

[0034] Returning to equation 1, X 1 is a group having a curable group. In this specification, the group having a curable group means the curable group itself or an atomic group having a curable group as a partial structure in its structure. X 1 The group having a curable group is not particularly limited, but is preferably a group represented by the following formula (III).

[0035] [ka]

[0036] In formula III, Z represents a curable group; L 3 represents a single bond or a divalent group. Also, "*" represents the bond position. L 3 The divalent group is not particularly limited, and may be -C(O)-, -C(O)O-, -OC(O)-, -O-, -S-, -NR 20 -(R 20 represents a hydrogen atom or a monovalent organic group), an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 10 carbon atoms), and combinations thereof. Among these, L is particularly preferred in that it can provide a member having the effects of the present invention. 3 is a single bond, -O-, -C(O)-, an alkylene group, or -NR 20- and combinations thereof are preferred.

[0037] In formula III, the curable group of Z refers to a group involved in a curing reaction. The curable group is not particularly limited, but is preferably a radical polymerizable group, and more preferably a group having an ethylenically unsaturated bond, in terms of obtaining a member having a better effect of the present invention. The group having an ethylenically unsaturated bond is not particularly limited, but includes, for example, a (meth)acryloyl group, a styryl group, and an allyl group, and among them, a (meth)acryloyl group is preferred. In this specification, "(meth)acryloyl" means either one or both of acryloyl and methacryloyl.

[0038] Returning to Equation 1, M 1 As the p+q valent group, M 1 When L is a divalent group, its form is not particularly limited, but 3 The divalent groups already explained above are preferred.

[0039] M 1 When is a trivalent or higher valent group, there is no particular limitation, and examples thereof include groups represented by the following formulas (4a) to (4d). [ka]

[0040] In formula 4a, L3 represents a trivalent group. T3 represents a single bond or a divalent group, and three T3 may be the same or different. Examples of L3 include a nitrogen atom, a trivalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or a trivalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Specific examples of L3 include a glycerol residue, a trimethylolpropane residue, a phloroglucinol residue, and a cyclohexanetriol residue.

[0041] In formula 4b, L4 represents a tetravalent group. T4 represents a single bond or a divalent group, and the four T4 may be the same or different. Suitable forms of L4 include a tetravalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group) and a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Specific examples of L4 include a pentaerythritol residue and a ditrimethylolpropane residue.

[0042] In formula 4c, L5 represents a pentavalent group. T5 represents a single bond or a divalent group, and five T5 may be the same or different. Suitable forms of L5 include pentavalent hydrocarbon groups (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic or aliphatic hydrocarbon group) or pentavalent heterocyclic groups (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Specific examples of L5 include an arabinitol residue, a phloroglucidol residue, and a cyclohexanepentanol residue.

[0043] In formula 4d, L6 represents a hexavalent group. T6 represents a single bond or a divalent group, and six T6 may be the same or different. Suitable forms of L6 include a hexavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic or aliphatic hydrocarbon group) or a hexavalent heterocyclic group (preferably a 6- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (e.g., -O-). Specific examples of L6 include a mannitol residue, a sorbitol residue, a dipentaerythritol residue, a hexahydroxybenzene residue, and a hexahydroxycyclohexane residue.

[0044] In the formulae 4a to 4d, the divalent groups represented by T3 to T6 are the same as those already described above. 1It may be the same as or the same as the divalent group. Also, M 1 When is a group with a valence of 7 or more, a group formed by combining the groups represented by formulae 4a to 4d can be used.

[0045] Returning to formula 1, p1 represents an integer of 0 or more, preferably 2 or less, more preferably 1 or less, and further preferably 0. In addition, q1 represents an integer of 2 or more, preferably 4 or less, more preferably 3 or less, and further preferably 2.

[0046] In formula 1, R 1 represents a hydrogen atom or a monovalent substituent not having the above-mentioned curable group. The monovalent substituent not having a curable group is not particularly limited, and examples thereof include a group represented by *-L"-R'. In the above formula, L″ represents a single bond or a divalent group, R′ represents a hydrogen atom or a hydrocarbon group (which may be linear, branched, or cyclic), and * represents the bonding position.

[0047] The curable compound 1 is preferably a compound represented by the following formula 1B, in that a cured product having better effects of the present invention can be obtained.

[0048] [ka]

[0049] In formula 1B, M 1B is a 1-valent group, and its form, including the preferred form, is the same as that of M in formula 1 already described. 1 The above is the same as the group represented by the following formula: L 1B represents a poly(oxyalkylenecarbonyl) group, and X 1B represents a group having a curable group, and the form thereof, including the preferred form, is the same as that of L in Formula 1 already described above. 1 , and X 1 is the same as:

[0050] In order to obtain a member having even more excellent effects of the present invention, the curable compound is preferably a compound represented by the following formula 1D.

[0051] [ka]

[0052] In formula 1D, AL 2 represents an alkylene group having 1 to 20 carbon atoms. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 3 or more and 10 or less. D represents a hydrocarbon having 1 to 5 carbon atoms, and is preferably at least one group selected from the group consisting of -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2C(CH3)2CH2-, and more preferably -CH2CH2CH2CH2-. X 1D represents a group having a curable group, and its form, including the preferred form, is the same as X in formula 1 described above. 1 The above is the same as the group represented by the following formula:

[0053] In formula 1D, w represents an integer of 2 or more, preferably an integer of 100 or less, more preferably an integer of 50 or less, and more preferably an integer of 20 or less.

[0054] The number average molecular weight of the curable compound 1 is not particularly limited, but in general, a value of 2,000 to 8,000 is preferred. Furthermore, the molecular weight distribution (Mw / Mn) of the curable compound is not particularly limited, but is generally preferably 1.1 to 1.6. The number average molecular weight and weight average molecular weight of the curable compound 1 refer to values ​​determined by GPC (Gel Permeation Chromatography) measurement according to the method described in the Examples below.

[0055] <Curable compound 2> The composition includes a curable compound 2 represented by the following formula 2: The content of the curable compound 2 in the composition is not particularly limited, but in relation to the curable compound 1 described later, when the total is taken as 100 mol%, the content is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 15 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 65 mol% or less, and particularly preferably 60 mol% or less.

[0056] In particular, when the cured product is to be actuated on the surface of a living body, the content of the curable composition 2 is preferably 40 to 55 mol %. When the cured product is driven in a living body, the content of the curable composition 2 is preferably from 1 to 40 mol %, and more preferably from 15 to 40 mol %.

[0057] [ka]

[0058] L 2 represents a polymer chain, the polymer chain including a repeating unit composed of an oxyalkylenecarbonyl group, a repeating unit derived from D-lactic acid, and a repeating unit derived from L-lactic acid; 2 is X in Equation 1 1 represents a group having the same curable group as that represented by R 2 represents a hydrogen atom or the above-mentioned monovalent substituent not having a curable group, q2 represents an integer of 2 or more, p2 represents an integer of 0 or more, and when q2 is 2 and p2 is 0, M 2 represents a single bond or a divalent group, and when q2 is 2 and p2 is 1 or more, and when q2 is 3 or more, M 2 represents a p2+q2-valent group, and multiple R 2 , and L 2 may be the same or different.

[0059] L in Equation 1 2 The polymer chain of is a polymer chain that contains all of the repeating units consisting of oxyalkylenecarbonyl groups, the repeating units derived from D-lactic acid, and the repeating units derived from L-lactic acid. 2The polymer chain may have repeating units other than those mentioned above, in which case it is preferably a poly(oxyalkylene) group (chain).

[0060] Lactic acid exists as two optical isomers, L-lactic acid and D-lactic acid, which are represented by the following formula. Polylactic acid polymers can be obtained by polyesterification of these.

[0061] Typically, lactic acid can be polymerized by being converted to a cyclic lactide as shown in the following formula and then subjected to ring-opening polymerization. In this specification, the repeating unit of the polymer derived from this D-lactic acid is referred to as a "repeating unit derived from D-lactic acid" and the repeating unit of the polymer derived from L-lactic acid is referred to as a "repeating unit derived from L-lactic acid."

[0062] [ka]

[0063] Therefore, L 2 The polymer chain has a repeating unit P1 (a repeating unit consisting of an oxyalkylene carbonyl group) represented by the following formula, P2D (a repeating unit derived from D-lactic acid), and P2L (a repeating unit derived from L-lactic acid). In the following formula, n represents an integer of 1 to 20, preferably an integer of 2 to 10, and more preferably an integer of 3 to 8. [ka]

[0064] L 2 The order of arrangement of the P1 unit, P2D unit, and P2L unit in the polymer chain is not particularly limited, and may be random, triblock, or multiblock. 2From the viewpoint of easily controlling the melting point of the polymer chain of L2 to a lower level, it is preferable that the polymer chain is arranged randomly (a random copolymer). The polymer chain of L2 becomes a polymer chain located between crosslinking points in the cured product (crosslinked body), but if the arrangement of the repeating units of this polymer chain is random, the polymer chain is unlikely to have a regular folded structure or an extended chain structure, and the melting point of the cured product becomes lower or the cured product does not have a melting point (does not have crystallinity).

[0065] L 2 The contents of P1 units, P2D units, and P2L units in the above-mentioned copolymer are not particularly limited, but when the total content of each unit is taken as 100 mol%, the content of P1 units is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, particularly preferably 40 mol% or more, most preferably 50 mol% or more, and is preferably 90 mol% or less, and more preferably 80 mol% or less. Furthermore, the contents of the P2D units and the P2L units are each preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more, and are preferably 30 mol % or less, and more preferably 20 mol % or less.

[0066] The repeating numbers of the P1 unit, P2D unit, and P2L unit in the polymer chain are not particularly limited, but from the viewpoint of making the deformation rate of the cured product larger, the repeating number is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, and is preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less.

[0067] Returning to Equation 2, X 2 is a group having a curable group. 2 The curable group contained in the compound represented by the formula 1 is X 1 In addition, X 2 Specific examples of the group X 1 The preferred embodiments are also the same as those of the group represented by the formula (I). Also, R 2 The monovalent substituent of R in formula 1 is also 1 The monovalent substituents are the same as those in the above, and the preferred embodiments are also the same. Also, M 2 The divalent group and the trivalent or higher group are also represented by M 1 The divalent group and the trivalent or higher valent group are the same as those mentioned above, and the preferred embodiments are also the same.

[0068] In formula 2, p2 represents an integer of 0 or more, preferably 2 or less, more preferably 1 or less, and even more preferably 0. Furthermore, q2 represents an integer of 2 or more, preferably 3 or more, preferably 8 or less, and more preferably 6 or less.

[0069] The curable compound 2 is preferably a compound represented by the following formula 1C, in that a cured product having better effects of the present invention can be obtained.

[0070] [ka]

[0071] In formula 1C, M 1C is a divalent group, L 1C represents a polymer chain, the polymer chain containing all of a repeating unit consisting of an oxyalkylenecarbonyl group, a repeating unit derived from D-lactic acid, and a repeating unit derived from L-lactic acid (and may further contain a poly(oxyalkylene) group); X 1C is X in formula 1B 1B represents a group having the same curable group as that represented by r2, r2 represents an integer of 2 or more, and 1C may be the same or different.

[0072] Here, L 1C Polymer chain, M1 C a divalent or trivalent or higher group, X 1C The curable group is L in formula 2. 2 Polymer chain, M 2 a divalent or trivalent or higher group, X 2 The curable groups are the same as those in the above, and the preferred forms are also the same. r2 is preferably an integer of 2 or more, and is preferably not more than 10, more preferably not more than 8, and even more preferably not more than 6. When r2 is within the above numerical range, a cured product having better effects of the present invention can be obtained.

[0073] From the viewpoint of obtaining a cured product having a more excellent effect of the present invention, the curable compound 2 is preferably a compound represented by the following formula 1E.

[0074] [ka]

[0075] In formula 1E, L 1Ea represents a polymer chain, and includes all of a repeating unit consisting of an oxyalkylenecarbonyl group, a repeating unit derived from D-lactic acid, and a repeating unit derived from L-lactic acid, 1Eb represents a single bond or a polymer chain consisting of a poly(oxyalkylene) group (chain), and X 1E is X in Equation 1D 1D represents a group having the same curable group as

[0076] Here, L 1E The polymer chain of X 1E The group having a curable group is represented by L in formula 2. 2 The polymer chain of X 2 The same groups as those having a curable group as mentioned above can be mentioned, and the preferred forms are also the same.

[0077] From the viewpoint of enabling the cured product to have both a lower melting point and a higher deformation rate, it is preferable that the test specimen prepared by the following method does not have crystallinity.

[0078] Preparation method of the test specimen: 500 mg of the curable compound 2, 15 mg of benzoyl peroxide, and 695 μL of xylene are mixed to obtain a composition, which is then heated to 80° C. to polymerize it. The resulting polymer is washed with acetone, shrunk in methanol, and then dried under reduced pressure to obtain a test specimen.

[0079] The number average molecular weight of the curable compound 2 is not particularly limited, but is generally preferably 8000 to 40000. The molecular weight distribution (Mw / Mn) of the curable compound is not particularly limited, but is generally preferably 1.10 to 1.80. The number average molecular weight and weight average molecular weight of the curable compound 2 refer to values ​​determined by GPC (Gel Permeation Chromatography) measurement according to the method described in the Examples below.

[0080] <Method of producing curable compound> Next, a method for producing the curable compound 1 and the curable compound 2 (collectively, simply referred to as "curable compound") will be described. The method for producing the curable compound is not particularly limited, but a method in which a group having a curable group is introduced into a precursor compound obtained by ring-opening polymerization of a cyclic compound is preferred in that the curable compound can be obtained more simply.

[0081] As the cyclic compound, a known cyclic compound can be used, and is not particularly limited, but is preferably one that can be ring-opened by hydrolysis. For example, cyclic esters (lactone compounds) such as β-propiolactone, β-butyrolactone, β-valerolactone, γ-butyrolactone, γ-valerolactone, γ-caprylolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoic lactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and α-methyl-γ-butyrolactone; cyclic diesters such as glycolide and lactide; and the like can be mentioned.

[0082] Among these, the cyclic compound is preferably a lactone compound or lactide in terms of good reactivity in ring-opening polymerization, and the lactone compound is more preferably at least one selected from the group consisting of β-propiolactone, β-butyrolactone, β-valerolactone, γ-butyrolactone, γ-valerolactone, γ-caprylolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, and ε-palmitolactone.

[0083] In particular, lactide can be used for the synthesis of the curable compound 2, and examples of this lactide include L-lactide (LL-lactide) formed by dehydration condensation of two molecules of L-lactic acid, D-lactide (DD-lactide) formed by dehydration condensation of two molecules of D-lactic acid, meso-lactide formed by dehydration condensation of one molecule of L-lactic acid and one molecule of D-lactic acid, and DL-lactide (racemic lactide) which is an equal mixture of D-lactide and L-lactide, etc. DL-lactide is preferred in that the melting point of the obtained cured product tends to be lower.

[0084] The method for obtaining a precursor compound by ring-opening polymerization of a cyclic compound is not particularly limited, but examples thereof include a method for ring-opening polymerization using an alcohol as an initiator in the presence of a metal catalyst.

[0085] Metal catalyst The metal catalyst is not particularly limited, but examples thereof include fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides, halides, and alcoholates of alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, and antimony. More specifically, examples of the compounds include stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, stannous myristate, stannous octoate (Tin (II)-ethylhexanoate), stannous stearate, tetraphenyltin, tin methoxide, tin ethoxide, stannous butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex, titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, zinc oxide, diethylzinc, antimony trioxide, antimony tribromide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, and yttrium alkoxide.

[0086] The amount of the metal catalyst used was 0.01 × 10 per mole of the cyclic compound, calculated as the metal element in the metal catalyst. -4 ~100×10 -4 Molar amounts are preferred.

[0087] Initiator The initiator is not particularly limited, but may be a monohydric or dihydric or higher alcohol.

[0088] The monohydric alcohol is not particularly limited, but R IN Alcohols represented by -OH are included, and R IN represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The aliphatic hydrocarbon group is not particularly limited, but examples thereof include alkyl groups having 1 to 20 carbon atoms. Examples of monohydric alcohols include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, pentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, octyl alcohol, nonyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, n-dodecyl alcohol, hexadecyl alcohol, lauryl alcohol, ethyl lactate, and hexyl lactate.

[0089] Examples of dihydric or higher alcohols (polyhydric alcohols) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and pentaerythritol ethoxylate.

[0090] Among these, dihydric alcohols or tetrahydric alcohols are preferred in that they give a cured product having better effects of the present invention, and the dihydric alcohol is preferably at least one selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol. As the tetrahydric alcohol, pentaerythritol, pentaerythritol ethoxylate, and the like are preferable. The amount of the initiator used is not particularly limited, but is preferably about 0.0001 to 0.1 mol per 1 mol of the cyclic compound.

[0091] ·Ring-opening polymerization The ring-opening polymerization is preferably carried out under an inert gas atmosphere in order to prevent the volatilization of the cyclic compound. The polymerization temperature is not particularly limited, but is preferably 100 to 250°C. The polymerization time is not particularly limited, but is preferably about 0.1 to 48 hours.

[0092] -Introduction of curable groups The method of introducing a curable group into a precursor compound obtained by ring-opening polymerization of a cyclic compound is not particularly limited, and examples thereof include a method (a) of reacting a compound having both a substituent reactive to a hydroxy group possessed by the precursor compound and a curable group, and a method (b) of substituting a hydroxy group possessed by the precursor compound with another functional group, and reacting a compound having both a functional group reactive to the substituent and a curable group, etc. Among them, the method (a) is preferred in that a curable compound (macromonomer) can be obtained more easily.

[0093] In the above method (i), the compound to be reacted with the hydroxy group of the precursor compound is not particularly limited, but examples thereof include unsaturated acid halogen compounds such as (meth)acrylic acid chloride and (meth)acrylic acid bromide when the curable group is a (meth)acryloyl group. The amount of the compound to be reacted with the hydroxy group of the precursor compound is not particularly limited, but is preferably about 0.1 to 20 molar equivalents relative to the hydroxy group.

[0094] The composition may contain other components as necessary, so long as it contains the curable compound 1 obtained by the method described above and the curable compound 2. Examples of the other components include a curing agent and a solvent.

[0095] <Hardening agent> A curing agent is a compound that acts on a curable compound to cause a curing reaction. The curing agent is not particularly limited, and known compounds can be used, typically radical polymerization initiators are preferred. As the curing agent, a heat curing agent in which a curing reaction proceeds by applying heat energy and / or a light curing agent in which a curing reaction proceeds by applying light (applying light energy) can be used.

[0096] Examples of the heat curing agent include azo compounds such as azobisisobutyronitrile, and peroxides such as benzoyl peroxide. Examples of the photocuring agent include aromatic ketone compounds such as benzophenone, Michler's ketone, xanthone, and thioxanthone; quinone compounds such as 2-ethylanthraquinone; acetophenone compounds such as acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzoin ether, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone; and methylbenzoyl formate. diketone compounds, such as 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime; acyloxime ester compounds, such as 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime; acylphosphine oxide compounds, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfur compounds, such as tetramethylthiuram and dithiocarbamate; organic oxides, such as benzoyl peroxide; azo compounds, such as azobisisobutyronitrile; organic sulfonium salt compounds; iodonium salt compounds; phosphonium compounds; and the like.

[0097] The content of the curing agent in the composition is preferably 0.001 to 10% by mass based on the total mass of the curable compounds in the composition. The composition may contain one type of curing agent alone or two or more types. When the composition contains two or more types of curing agents, the total content is preferably within the above numerical range.

[0098] <Solvent> The composition may contain a solvent. The solvent contained in the composition is not particularly limited, but it is sufficient to select a solvent that can dissolve and / or disperse the curable compound and the curing agent and that does not easily evaporate during the curing reaction. For example, when benzoyl peroxide (BPO) is used as a curing agent, the temperature of the curing reaction is about 80° C., so a solvent with a boiling point equal to or higher than the curing reaction temperature is preferred. By using such a solvent, evaporation of the solvent during the curing reaction can be further suppressed, so that a cured product with fewer air bubbles is likely to be obtained. Examples of such solvents include xylene, butyl acetate, DMF (N,N-dimethylformamide), and dimethyl sulfoxide.

[0099] On the other hand, when a photocuring agent is used as the curing agent, the temperature of the curing reaction is generally lower than when a thermal curing agent is used, so that even if a solvent with a lower boiling point is used, a cured product with fewer air bubbles can be obtained. Examples of the solvent that can be used include dichloromethane, chloroform, and acetone.

[0100] The content of the solvent in the composition is not particularly limited, but when the composition contains a solvent, it is preferably 10 to 90% by mass when the total mass of the composition is 100% by mass. The composition may contain one type of solvent alone, or may contain two or more types. When the composition contains two or more types of solvents, the total content is preferably within the above numerical range.

[0101] [Method for producing the cured product] There are no particular limitations on the method for producing the cured product, and it is sufficient to mix the above-mentioned components to obtain a composition, and then apply energy to the composition to cure the curable compound. In particular, in terms of obtaining a cured product having even more excellent effects of the present invention, the method for producing the cured product preferably includes the following steps.

[0102] Curing step: a step of applying energy to a composition containing a curable compound and a curing agent to cure the curable compound and obtain a cured product. Furthermore, the method for manufacturing the component may include the following steps. Drying step: a step of drying the cured product to remove at least a part of the solvent.

[0103] The curing step is a step of applying energy to a composition containing a curable compound and a curing agent to cure the composition. The type of energy applied may be appropriately selected depending on the type of curing agent, and heating and / or light irradiation are preferred.

[0104] The method for applying energy is not particularly limited, and examples thereof include a method in which a composition is applied onto a support to form a composition layer, and then the composition layer is irradiated with light and / or heated to obtain a film-like cured product. The heating temperature and time, the intensity of the light irradiation, and the like may be appropriately selected depending on the shape of the member, the type of the curing agent, and the like. More specifically, the heating temperature may be, for example, 40 to 200° C. Furthermore, the heating time may be, for example, 1 minute to 24 hours.

[0105] The drying step is a step of drying the cured product to remove at least a part of the solvent contained in the cured product. The drying method is not particularly limited, and examples thereof include a method of leaving the product at rest at 20 to 50°C for 1 minute to 24 hours and a method of holding the product under reduced pressure. The drying conditions may be appropriately selected depending on the shape and thickness of the cured product.

[0106] The size and shape of the present cured product are not particularly limited. They may be appropriately determined depending on the application. The present cured product has a shape memory function, a lower driving temperature, and an excellent deformation rate, and therefore can be applied to medical instruments such as ligatures and sutures. The present cured product can also be used as a film by taking advantage of its shape memory function. For example, if the film is used as the base material of an adhesive tape having a base material and an adhesive layer disposed on the base material, it can be preferably used as a medical tape.

[0107] [Method of using the cured product] The method of using the cured product is not particularly limited, but as described above, the cured product has a shape memory function. Therefore, the temporary shape can be fixed by heating the cured product under stress to its softening point (a temperature near the melting temperature of the crystal) and then cooling it. Then, when the part in the temporary shape is reheated to its softening point, it returns to its permanent shape.

[0108] [ligature tool] A ligature tool is an instrument used to ligate a biological protrusion such as a tumor or a polyp to cut off blood flow or to remove the biological protrusion. Since the present ligature tool comprises a hardened material having shape memory ability, it shrinks when heated (for example, by heating with body temperature), and a desired tightening force can be stably obtained.

[0109] The ligation tool according to the present invention will be described with reference to Figs. 1 to 4. Fig. 1 is a schematic plan view of one example of an embodiment of the ligation tool of the present invention, and Fig. 2 is a schematic front view of the ligation tool. The ligation tool 100 is ring-shaped and has an inner diameter that corresponds to the cross-sectional radius of the part to be ligated when ligated. The size, shape, etc. of the ligature tool are not limited to those described above and can be changed appropriately depending on the area to be ligated.

[0110] FIG. 3 is a schematic front view of ligature tool 100 after it has been spread out, heated to the softening point of the hardened material (a temperature close to the melting point), and then cooled to fix the temporary shape, and then wrapped around a biological part 101 to be ligated. Since the ligature 100 has a temporary shape, it returns to the temporary shape when heated (by body temperature) by the living body part 101 or when heated as necessary, i.e., returns to the shape before being unfolded.

[0111] FIG. 4 is a schematic front view showing a state in which a biological part 101 is ligated by the ligature tool 100 that has returned to its temporary shape. With this ligature tool, the target area can be tightened with a pre-designed tightening force with a simple operation (without requiring any special procedure).

[0112] [Sutures] The suture of the present invention is a suture containing the present cured product. A suture is a thread-like instrument used in surgery or the like for tying off blood vessels or suturing incised tissue or skin.

[0113] Because this suture contains a hardened material with shape memory ability, when it is stretched into a temporary shape by applying stress and then applied to the part to be sutured, it returns to its permanent shape, i.e., shrinks, due to body heat or heating, making it easy to suture the part.

[0114] Figure 5 is an image showing the temporary shape of the suture applied to an incision on the back of a Sprague-Dawley rat. The black thread-like material in the image is the suture. Figure 6 shows the suture shrinking (returning to its permanent shape) and closing the incision after the back of the SD rat was warmed by spraying it with 37°C water. As described above, when the present suture is used, the target site can be sutured simply and easily without the need for special procedures.

[0115] [Wearable devices] 6 shows an example of an embodiment of a wearable device of the present invention. A wearable device 60 has a main body 61 and a holder 62 for holding the main body 61 on the body of a user, and the holder 62 has the hardened material already described. The wearable device 60 is held on the arm of a user 63 by a holder 62 .

[0116] The main body 61 is a time display unit, but the wearable device according to the embodiment of the present invention is not limited to the above. For example, it may be a communication device such as a smartphone, or a measuring device for the user's biological information (vital data such as pulse, blood pressure, body temperature, and skin potential).

[0117] The retaining portion 62 is a film formed from the cured product already described and molded into a cylindrical shape, but the retaining portion of the wearable device according to an embodiment of the present invention is not limited to the above and may be any portion that has a cured product, for example, a laminate having a support and a cured product layer formed on at least one main surface of the support.

[0118] The cured product of the above composition is preferably one whose driving temperature is the temperature of the surface of a living body, and specifically, the peak melting temperature of the crystal is preferably 31.0 to 35.0°C. For example, the holding unit 62 is a wristband, which is heated and stretched, cooled, deformed to an inner diameter that fits the arm, and then worn on the arm. When the wristband is warmed again by body heat, the wristband shrinks and changes to an inner diameter that fits the arm perfectly. When the wristband is removed, it is already heated to above its softening temperature, so by stretching it, that part is cooled to room temperature (e.g., 25°C), the distortion is fixed, and the wristband is fixed in a larger inner diameter. Once in this state, the wristband can be removed from the user's arm. According to the above, a wearable device that fits snugly to the user's body shape, etc. can be provided without having to prepare wristbands of multiple lengths depending on the user's body shape, etc., or without adding a length adjustment function to the wristband. EXAMPLES

[0119] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0120] [Synthesis of curable compound 1 (2b20PCL macromonomer)] Curable compound 1 (2b20PCL macromonomer) was synthesized based on the following scheme. First, the divalent ring-opening polymerization initiators 1,4-butanediol (2.21 mL, 0.025 mol) and ε-caprolactone (CL) (105.6 mL, 1 mol) and the catalyst tin(II)-2 ethylhexanoate (0.2 mL) were added to a round-bottom flask and reacted at 120°C for 24 hours under a nitrogen atmosphere.

[0121] The reaction product was then reprecipitated in a mixed solvent of hexane and diethyl ether in a 1:1 volume ratio and dried under reduced pressure to obtain 2-branched 20-mer PCL (hereinafter also referred to as "2b20PCL").

[0122] Next, 10 times the amount of acryloyl chloride (17.7 mL, 0.055 mol) and 11 times the amount of triethylamine (33.2 mL, 0.060 mol) were added to the terminal group of the recovered 2b20PCL (50 g, 0.011 mol) and reacted for 72 hours. After that, it was purified by reprecipitation in methanol and dried under reduced pressure to recover the curable compound A (PCL macromonomer), which is a macromonomer of 2b20PCL.

[0123] [ka]

[0124] The molecular weight of "2b20PCL" and the number of repeating oxyalkylenecarbonyl groups were determined by GPC and 1 The test conditions were as follows: The number average molecular weight of 2b20PCL determined from the GPC results was 3700, and the Mw / Mn was 1.23.

[0125] GPC measurement conditions Measuring device: (Tosoh) HLC-8220GPC Detector: Refractive index (RI) detector Column used: "Shodex (trademark)" GPC LF-804 (80 mm I.D. x 300 mm x 2 columns) Column temperature: 40℃ Eluent: DMF (dimethylformamide), flow rate 0.5 mL / min Sample: Dissolve in DMF at 0.2% by mass and filter through a 0.45 μm membrane filter. Molecular weight standard polymer: polystyrene (molecular weight = 1970, 3930, 7920, 12140, and 21030), 0.1 mass%

[0126] ·NMR measurement conditions Measurement equipment: 400MHz NMR (JEOL) Solvent: Deuterated chloroform (CDCl3) Sample concentration: ~30mg / mL (3mass / vol%) Reference material: Tetramethylsilane (TMS) Measurement Method: 1 H measurement resonance frequency 400MHz Observed spectral width: 0ppm~10ppm Number of times accumulated: 128 times Measurement temperature: room temperature (20~25℃)℃

[0127] [Synthesis of curable compound 2 (4b50P(CL-co-DLLA))] Based on the following scheme, the synthesis of curable compound 2 (a copolymer of CL and d,l-lactide (DLLA)) was carried out. First, the tetravalent ring-opening polymerization initiator pentaerythritol (343 mg, 0.005 mol), ε-caprolactone (32 mL, 0.3 mol), DLLA (14.5 g, 0.2 mol), and catalyst Tin(II) 2-ethylhexanoate (0.2 mL) were added to a round-bottom flask and reacted at 140°C for 24 hours under a nitrogen atmosphere to obtain 4-branched 50-mer P(CL-co-DLLA). Hereinafter, this will be referred to as "4b50P(CL-co-DLLA)".

[0128] Then, 10 times the amount of acryloyl chloride and 11 times the amount of triethylamine were added to the terminal group, and the mixture was allowed to react for 72 hours. After that, the mixture was purified by reprecipitation in methanol and dried under reduced pressure to recover the curable compound 2 (4b50P(CL-co-DLLA) macromonomer), which is a macromonomer of 4b50P(CL-co-DLLA). In the following scheme, m:n is a molar ratio of 6:4.

[0129] The number average molecular weight of 4b50P (CL-co-DLLA) measured by GPC was 9900, and the Mw / Mn was 1.44.

[0130] [ka]

[0131] [Preparation of cured product] A composition was prepared using the curable compound 1 and the curable compound 2, and the composition was heated and cured to obtain a cured product. Table 1 shows the composition formulation. A composition was obtained by completely dissolving 500 mg of the curable compounds 1 and 2 in total, and 15 mg of benzoyl peroxide (3 mass / volume % of the total of the curable compounds) as a radical polymerization initiator (curing agent) in 695 μL of xylene.

[0132] Next, this composition was dropped onto a glass substrate, sandwiched between another glass substrate via a 0.2 mm thick polytetrafluoroethylene spacer, and left to stand overnight (3 hours or more) in an oven at 80° C. to cure. The resulting cured product was thoroughly washed with acetone, shrunk in methanol, and then dried under reduced pressure (overnight).

[0133] [DSC measurement] DSC measurements were performed to measure the melting peak temperature and crystallinity of the crystals of the obtained cured product. The DSC measurements were performed using a differential scanning calorimeter (heat flux type) "X-DSC 7000" manufactured by SII Corporation. The test conditions were as follows.

[0134] Measurement container: Aluminum sample pan (φ6.8mm) Sample amount and size: The sample amount was approximately 10 mg, and was cut to fit into the sample pan.

[0135] Starting temperature: 0℃ Heating rate: 5℃ / min End temperature: 120℃

[0136] First, each sample (cured material) was heated from room temperature to 120°C, and when it reached 120°C, it was cooled to -5°C. Next, after the temperature of the sample reached -5°C, it was heated from 0°C to 120°C at a rate of 5°C / min, and the DSC curve was obtained.

[0137] The melting peak temperature (Tm) of the crystals read from the obtained DSC curve and the degree of crystallinity are shown in Table 1. The degree of crystallinity was calculated by calculating the enthalpy (ΔH) from the endothermic peak area, and then the formula (degree of crystallinity) = (ΔH / 142) x 100. Each value was calculated to two decimal places and rounded off.

[0138] [Measurement of elastic modulus] The elastic modulus was calculated from the linear portion of the stress-strain curve obtained by the tensile test. The test piece was in the form of a sheet with a length of 17.5±2.5 mm, a width of 5.00±0.90 mm, and a thickness of 0.14±0.30 mm. The test was performed at room temperature with a tensile speed of 5 mm / min. Each value was calculated to two decimal places and rounded off.

[0139] The lower the elastic modulus, the greater the deformation when the same force is applied. The higher the breaking strain, the less likely the cured material is to break even when subjected to a large deformation. From the above, a cured material with both a smaller elastic modulus and a larger breaking strain has a larger deformation rate as a shape memory material. In addition, the "ratio" in Table 1 indicates the molar ratio of the content of curable compound 2 to the contents of curable compound 1 and curable compound 2 in the composition ([curable compound 2] / [curable compound 1 + curable compound 2]). In addition, in Table 1, "-" indicates that no data is available (no crystallinity and no melting point).

[0140] [Table 1]

[0141] From the results in Table 1, it can be seen that the cured products obtained by curing the compositions containing Curable Composition 1 and Curable Composition 2 were all crystalline, had a small elastic modulus, a large breaking strain, and had a large deformation rate as shape-memory materials. On the other hand, the cured product of Example 1C obtained by curing a composition containing only Curable Composition 1 had a large elastic modulus and a small deformation rate as a shape-memory material. Furthermore, the cured product of Example 2C obtained by curing a composition containing only Curable Composition 2 did not have crystallinity and did not exhibit shape-memory ability.

[0142] The cured product of the composition of Example 4, in which the above ratio was 0.15 to 0.40, had a higher peak melting temperature (Tm) of the crystals than the cured product of the composition of Example 1, and a lower peak melting temperature (Tm) of the crystals than the cured product of the composition of Example 5, both of which were 35.0 to 43.0°C, and were therefore more suitable for applications in which the crystals would be driven within a living body (such as a ligature).

[0143] Furthermore, the cured product of the composition of Example 1, in which the above ratio was 0.40 to 0.55, had a lower crystal melting peak temperature (Tm) of 32.0 to 35.0°C compared to the cured product of the composition of Example 2, and was therefore more suitable for applications in which the material is driven on the surface of a living body (wearable devices, sutures, etc.).

[0144] Furthermore, the cured product of the composition of Example 1, which had a crystallinity of 10.0 to 15.0%, had a lower crystal melting peak temperature (Tm) of 32.0 to 35.0°C compared to the cured product of the composition of Example 2 and the cured product of the composition of Example 2, making it more suitable for applications that are driven on the surface of a living body (wearable devices, sutures, etc.).

[0145] Furthermore, the cured product of the composition of Example 4, which had a crystallinity of 15.0 to 20.0%, had a higher peak melting temperature (Tm) of the crystals than the cured product of the composition of Example 1, and a lower peak melting temperature (Tm) of the crystals than the cured product of the composition of Example 5, both of which were 35.0 to 43.0°C, making them more suitable for applications in vivo (such as ligatures). [Industrial Applicability]

[0146] The present cured product has a shape memory function, a lower operating temperature, and an excellent deformation rate, and therefore can be applied to medical instruments such as ligatures and sutures. The present cured product can also be used as a film by taking advantage of its shape memory function. For example, if the film is used as the base material of an adhesive tape having a base material and an adhesive layer disposed on the base material, it can be preferably used as a medical tape. [Explanation of symbols]

[0147] 60: Wearable devices 61: Main body 62: Holding part 63:User 100: Ligating device 101:Body parts

Claims

1. A crystalline cured product obtained by curing a composition containing a curable compound 1 represented by the following formula 1D and a curable compound 2 represented by the following formula 2. 【Chemistry 1】 (In formula 1D, AL 2 represents an alkylene group having 1 to 20 carbon atoms, X 1D represents a group having an ethylenically unsaturated bond, L D represents a hydrocarbon group having 1 to 5 carbon atoms, and w represents an integer of 2 to 100.) 【Chemistry 2】 (In formula 2, L ２ represents a polymer chain, the polymer chain including a repeating unit (I) consisting of an oxyalkylenecarbonyl group, a repeating unit (II) derived from D-lactic acid, and a repeating unit (III) derived from L-lactic acid, the repeating units (I) to (III) being randomly arranged and ester-bonded, X ２ represents a group having the same ethylenically unsaturated bond as X 1D in formula 1D, and is bonded to an oxygen atom of the polymer chain of L 2 , R ２ represents a hydrogen atom or a monovalent substituent that does not have a group having an ethylenically unsaturated bond, and is bonded to an oxygen atom of the polymer chain of L 2 , q ２ represents an integer of 2 or more; p ２ represents an integer of 0 or more; q ２ 2 and p ２ When is 0, M ２ represents a single bond or a divalent group; q ２ 2 and p ２ is 1 or more, and q ２ When is 3 or more, M ２ H ２ +q ２ R represents a valence group, ２ , and L ２ may be the same or different)

2. The cured product according to claim 1, wherein the molar ratio of the content of the curable compound 2 to the total content of the curable compound 1 and the curable compound 2 is 0.01 to 0.

65.

3. 3. The cured product according to claim 1, wherein the total number of repeating units in the polymer chain consisting of the oxyalkylene carbonyl group, the repeating unit derived from the D-lactic acid, and the repeating unit derived from the L-lactic acid is 10 to 100.

4. The cured product according to any one of claims 1 to 3, wherein the curable compound 2 is represented by the following formula 1C. 【Chemistry 3】 (In formula 1C, M １Ｃ is a divalent group, L １Ｃ represents a polymer chain, the polymer chain including a repeating unit (I) consisting of an oxyalkylenecarbonyl group, a repeating unit (II) derived from D-lactic acid, and a repeating unit (III) derived from L-lactic acid, the repeating units (I) to (III) being randomly arranged and ester-bonded, X １Ｃ represents a group having the same ethylenically unsaturated bond as X 1D in formula 1D, and is bonded to an oxygen atom of the polymer chain of L 1C , r2 represents an integer of 2 or more, and １Ｃ may be the same or different.)

5. The cured product according to any one of claims 1 to 4, wherein a test specimen prepared by the following method has no crystallinity. (Method of preparing a test specimen: 500 mg of the curable compound 2, 15 mg of benzoyl peroxide, and 695 μL of xylene are mixed to obtain a composition, which is heated to 80° C. to polymerize it, and the obtained polymer is washed with acetone, shrunk in methanol, and then dried under reduced pressure to obtain a test specimen.)

6. In formula 1D, the hydrocarbon group represented by L D is -CH ２ CH ２ --, --CH ２ CH ２ CH ２ --, --CH ２ CH ２ CH ２ CH ２ - and -CH ２ C (CH ３ ) ２ CH ２ The cured product according to any one of claims 1 to 5, wherein the aryl group is 0 or 1.

7. The cured product according to any one of claims 1 to 6, wherein the curable compound 2 is represented by the following formula 1E. 【Chemistry 4】 (In formula 1E, L １Ｅa represents a polymer chain, the polymer chain including a repeating unit (I) consisting of an oxyalkylenecarbonyl group, a repeating unit (II) derived from D-lactic acid, and a repeating unit (III) derived from L-lactic acid, the repeating units (I) to (III) being randomly arranged and ester-bonded, L １Ｅｂ represents a single bond or a polymer chain consisting of a poly(oxyalkylene) group, X １Ｅ is the X in formula 1D １Ｄ represents a group having the same ethylenically unsaturated bond as that of L 1Ea, and is bonded to an oxygen atom of the polymer chain of L 1Ea.

8. The cured product according to claim 2, wherein the ratio is from 0.15 to 0.

60.

9. The cured product according to claim 8, wherein the ratio is from 0.15 to 0.

40.

10. The cured product according to claim 8, wherein the ratio is from 0.40 to 0.

55.

11. The cured product according to any one of claims 1 to 10, having a crystallinity of 10.0 to 24.0%.

12. The cured product according to claim 11, wherein the crystallinity is 15.0 to 20.0%.

13. The cured product according to any one of claims 1 to 12, having a crystal melting peak temperature of 36.0 to 42.0 as measured by a differential scanning calorimeter.

14. A shape-memory member comprising the cured product according to any one of claims 1 to 13.

15. A ligature comprising the shape memory member according to claim 14.

16. A suture comprising the shape memory member of claim 14.

17. A wearable device comprising the shape memory member according to claim 14.

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