WO2021200532A1 - Member, method for manufacturing member, method for manufacturing permanent-shape-changed member, permanent-shape-changed member, cell culture substrate, ligation device, and laminate - Google Patents

Abstract

A member comprising: a cured article which is produced by curing a curable compound represented by formula 1 and has crystallinity; and a transesterification catalyst. (In formula 1, L1 represents a polyoxyalkylenecarbonyl group; X1 represents a group having a curable group; R1 represents a hydrogen atom or a monovalent substituent not having the curable group; q represents an integer of 2 or more; p represents an integer of 0 or more; when q is 2 and p is 0, M1 represents a single bond or a bivalent group; when q is 2 and p is 1 or more and when q is 3 or more, M1 represents a group having a valency of p+q; R1's may be the same as or different from each other; L1's may be the same as or different from each other; and X1's may be the same as or different from each other.)

Description

Member, method of manufacturing member, method of manufacturing permanent shape-changed member, permanent shape-changed member, cell culture substrate, ligation device, and laminate

The present invention relates to a member, a method for manufacturing a member, a method for manufacturing a member whose permanent shape has been changed, a member whose permanent shape has been changed, a cell culture substrate, a ligation device, and a laminate.

Aliphatic polyester resins such as polycaprolactone are known to have excellent biodegradability, and research is underway. Non-Patent Document 1 describes a temperature-responsive poly (ε-caprolactone) film.

The film described in Non-Patent Document 1 is deformed by an external force, and from a "temporary" shape (hereinafter, also simply referred to as "T shape") to which it is fixed, a "permanent (hereinafter, also simply referred to as" T shape ")" before being deformed. It had an excellent feature that the shape change to "Permanent)" shape (hereinafter, also simply referred to as "P shape") was caused by heating. In other words, it had the shape memory ability to return from the T shape to the original P shape.

However, the P shape depends on the original shape of the film (shape at the time of molding) and cannot be changed after the film is molded.
More specifically, in the film described in Non-Patent Document 1, the T shape can be variously changed depending on the method of deformation, but the P shape when returned after being heated is the shape when the film was originally molded. Depends on and could not be changed.

Therefore, in order to obtain a member having a three-dimensional shape having a curved surface as a P shape, for example, a mold having a cavity corresponding to the three-dimensional shape is prepared, and a composition containing a curable compound in the mold is prepared. It was complicated because it had to be filled and the composition had to be cured and molded.

In view of the above problems, it is an object of the present invention to provide a member having a shape memory ability that can easily adjust a permanent shape (P shape).
Another object of the present invention is to provide a method for manufacturing a member, a method for manufacturing a permanent shape-changed member, a permanent shape-changed member, a cell culture substrate, a ligation device, and a laminate.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.

[1]
A cured product having crystallinity obtained by curing a curable compound represented by the formula 1 and a cured product.
A member containing a transesterification catalyst.

(In Formula 1, L ¹ represents a polyoxyalkylene carbonyl group, X ¹ represents a group having a curable group, and R ¹ represents a hydrogen atom or a monovalent substituent having no curable group. Represented, q represents an integer of 2 or more, p represents an integer of 0 or more, and when q is 2 and p is 0, M ¹ represents a single bond or a divalent group, q is 2 and p. When is 1 or more and when q is 3 or more, M ¹ represents a group of p + q valence, and a plurality of R ¹ , L ¹ , and X ¹ may be the same or different, respectively.)
[2]
The member according to [1], further containing a polymer compound having a repeating unit composed of an oxyalkylene carbonyl group and having at least two or more hydroxy groups in the molecule.
[3]
The member according to [1] or [2], which has a shape memory ability.
[4]
The member according to any one of [1] to [3], wherein an endothermic peak is observed at 35 to 60 ° C. in the process of raising the temperature of the differential scanning calorimetry.
[5]
The member according to any one of [1] to [4], wherein the curable compound is represented by the following formula 1B.

(In formula 1B, M ^1B is an r-valent group, L ^1B represents a polyoxyalkylene carbonyl group, X ^1B represents a group having a curable group, r represents an integer of 2 or more, and there are a plurality of them. L ^1B and X ^1B may be the same or different from each other.)
[6]
The member according to any one of [1] to [5], wherein the curable compound is represented by the following formula 1C.

(In Formula 1C, AL ¹ represents a linear or branched alkylene group, X ^1C represents a group having a curable group, and t represents a number from 2 to 100.)
[7]
The member according to any one of [1] to [5], wherein the curable compound is represented by the following formula 1D.

(In Formula 1D, AL ² represents a linear or branched alkylene group, X ^1D represents a group having a curable group, and w represents a number from 2 to 100.)
[8]
The member according to any one of [1] to [7], wherein the polymer compound is represented by the following formula 2.

(In Formula 2, L ² represents a polyoxyalkylene carbonyl group, Y ² represents a group having a hydroxy group, R ² represents a hydrogen atom or a monovalent substituent having no hydroxy group, and n2. Represents an integer of 2 or more, m2 represents an integer of 0 or more, and when n2 is 2 and m2 is 0, M ² represents a single bond or a divalent group, n2 is 2 and m2 is 1 or more. When, and when n2 is 3 or more, M ² represents a group of m2 + n2 valence, and a plurality of L ² , R ² , and Y ² may be the same or different, respectively.)
[9]
The member according to any one of [1] to [8], wherein the polymer compound is represented by the formula 2B.

(In Formula 2B, L ^2B represents a polyoxyalkylene carbonyl group, Y ^2B represents a group having a hydroxy group, n _2B represents an integer of 2 or more, M ² represents a group having an n _2B valence, and there are a plurality of them. L ^2B and Y ^2B may be the same or different, respectively.)
[10]
The member according to any one of [1] to [9], wherein the polymer compound is represented by the formula 2C.

(In the formula 2C, AL ³ represents a linear or branched alkylene group, and g represents a number from 2 to 100.)
[11]
The member according to any one of [1] to [9], wherein the polymer compound is represented by the formula 2D.

(In the formula 2D, AL ³ represents a linear or branched alkylene group, and h represents a number of 2 or more.)
[12]
The member according to any one of [1] to [11], wherein the transesterification catalyst contains tin.
[13]
The method for manufacturing a member according to any one of [1] to [12].
An energy is applied to a composition containing the curable compound, the polymer compound, and a curing agent to cure the curable compound to obtain a cured product containing the polymer compound.
A method for producing a member, which comprises contacting a solution containing the transesterification catalyst and a solvent with the cured product to obtain a member.
[14]
A method for manufacturing a permanent shape-changed member, wherein the member according to any one of [1] to [12] is heated under stress and transesterified to obtain a permanent shape-changed member.
[15]
A method for changing the permanent shape of a member, wherein the member according to any one of [1] to [12] is heated under stress and subjected to a transesterification reaction to obtain a member whose permanent shape has been changed.
[16]
A permanent shape-changed member obtained by heating the member according to any one of [1] to [12] under stress and performing a transesterification reaction.
[17]
[16] A method for manufacturing a changed member having a different permanent shape, wherein the changed member having the permanent shape is heated under stress and transesterified to obtain a changed member having a different permanent shape.
[18]
[16] A method of changing a permanent shape of a member to a different permanent shape by heating the permanent shape-changed member under stress and causing a transesterification reaction to obtain a changed member having a different permanent shape.
[19]
A member that has been changed to a different permanent shape, which is obtained by heating the member whose permanent shape has been changed according to [16] under stress and performing a transesterification reaction.
[20]
The member according to any one of [1] to [12], [16] and [19] having a permanent shape is deformed into a temporary shape at a temperature of 100 ° C. or lower under stress, and then the crystal melting point of the member or higher. A method of returning the temporary shape of a member to the permanent shape by heating to a temperature of less than 120 ° C.
[21]
A cell culture substrate having the member according to any one of [1] to [12], [16] and [19].
[22]
A ligation device having the member according to any one of [1] to [12], [16] and [19].
[23]
A laminate having the member according to any one of [1] to [12], [16] and [19], and an adhesive layer arranged on the member.

According to the present invention, it is possible to provide a member having a shape memory ability that can easily adjust the P shape. The member may also have self-healing and recycling properties. Further, according to the present invention, it is also possible to provide a method for manufacturing a member, a method for manufacturing a member whose permanent shape has been changed, a member whose permanent shape has been changed, a cell culture substrate, a ligation device, and a laminate.

It is a perspective view of the cell culture substrate which is one Embodiment of this invention. This is an example of how to use the cell culture substrate. It is a schematic diagram of the ligation device which is one Embodiment of this invention. This is a procedure for ligating a living tissue using a ligation device. It is a schematic cross-sectional view of the laminated body which concerns on one Embodiment of this invention. Is a ^{1 H-NMR (Nuclear Magnetic Resonance} ) spectrum of 4B10PCL. It is a 1H-NMR spectrum of 2b20PCL. It is a figure which shows the attribution of each peak of NMR in the structural formula of 4b10PCL. It is a DSC curve (cooling process and temperature raising process) of the member 6. It is a DSC curve of the member C1. It is a DSC curve of a member 1. It is a DSC curve of a member 11. It is a DSC curve of a member 12. It is a DSC curve of a member 13. It is an image of the member 1 (P shape) immediately after preparation. It is an image of a member 1 in a state where it is spirally wound around a rod made of polytetrafluoroethylene and the end portion is fixed with a clip. It is an image of the member 1 after being held at 140 ° C. and cooled in the state of FIG. It is an image of a member 1 in a state where it is wound and fixed to a rod made of polytetrafluoroethylene along a direction in which the longitudinal direction of the rod and the longitudinal direction of the member 1 are substantially orthogonal to each other. It is an image of the member 1 after being held at 140 ° C. and cooled in the state of FIG. It is an image of a member 1 sandwiched between sheets made of polytetrafluoroethylene, folded in an M shape along the longitudinal direction, and fixed. It is an image of the member 1 after being held at 140 ° C. and cooled in the state of FIG. 20. It is an image of a member 1 having a spiral P shape, which was used for evaluation of shape memory ability. It is an image of the member 1 in the stretched state. It is an image of the member 1 after heating the member 1 of FIG. 23 to 60 degreeC. It is a thermomechanical analysis curve of member 1. It is a thermomechanical analysis curve of member 6. It is a thermomechanical analysis curve of the member C1. It is a figure which shows the disjointed state of the member 1 (the figure on the left), and the sample after pressure heat treatment (the figure on the right).

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

(Definition of terms)
In the present specification, the permanent shape (also referred to as “P shape”) means a state in which internal (residual) stress is relaxed, in other words, the most thermodynamically stable shape, and typically. It means a shape obtained when a member is heated to a temperature higher than the melting temperature of a crystal without applying stress from the outside and then cooled to room temperature.
The melting temperature of the crystal means the temperature of the peak top of the endothermic peak in the process of measuring the differential scanning calorimetry of the member (heating rate 10 ° C./min) (when having a plurality of endothermic peaks). , The peak top temperature of the peak on the hottest side).
The melting temperature "or more" may be about the terminal temperature on the high temperature side of the endothermic peak of the differential scanning calorimetry.
Further, the differential scanning calorimetry of the member shall be performed by the method described in Examples described later.

In the present specification, the temporary shape (also referred to as “T shape”) is a state in which the crystal is deformed by applying stress from the outside, and after heating to a temperature equal to or higher than the melting temperature of the crystal, the temperature reaches about (or lower) the crystallization temperature. It means the shape when the deformation is temporarily fixed by crystallization or the like by being cooled.
The crystallization temperature means the temperature of the peak top of the exothermic peak in the cooling process of measuring the differential scanning calorimetry of the member (cooling temperature 10 ° C./min).
Further, the differential scanning calorimetry of the member shall be performed by the method described in Examples described later.

[Element]
The member according to the present invention (hereinafter, also referred to as “the present member”) contains a cured product having crystallization obtained by curing a curable compound represented by the formula 1 described later, and a transesterification catalyst. It is a member. This member has a repeating unit consisting of an oxyalkylene carbonyl group; * -O-RC (= O)-* (R represents an alkylene group and * represents a bond position), and has at least 2 in the molecule. It is preferable to further contain a polymer compound having one or more hydroxy groups.

The mechanism by which the effects of the present invention are obtained by the above members is not always clear, but the present inventors speculate as follows. The mechanism described below is a presumption when the present member contains the above-mentioned polymer compound, and even when the problem of the present invention is solved by a mechanism other than the following mechanism. Members having the above configuration are included in the scope of the present invention.

Since the polymer compound contained in this member has a repeating unit composed of an oxyalkylene carbonyl group, it is highly compatible with the curable compound represented by the formula 1 described later. Therefore, it is presumed that when the polymer compound is composited with the cured product, the polymer compound is likely to be uniformly dispersed in the cured product.
That is, it is presumed that a semi-interpenetrating polymer network structure (semi-IPN, IPN is an abbreviation for intermediate polymer network) in which polymer compounds are entangled in a network of cured products (three-dimensional network structure) is likely to be formed.

Further, the above-mentioned polymer compound has a hydroxy group, and when heated to a predetermined temperature, transesterification is performed between the (poly) oxyalkylene carbonyl group of the cured product and the above-mentioned hydroxy group by the action of the transesterification catalyst. It is presumed that a reaction will occur.
Further, the polymer compound has at least two or more hydroxy groups in the molecule. Therefore, it is presumed that the transesterification reaction causes a structural change such as a recombination of the crosslinked structure between the cured product and the polymer compound.

When this member is stressed so as to have a desired P shape and a transesterification reaction is caused under the stress, the transesterification reaction causes a reaction such as the above-mentioned recombination of the crosslinked structure, so that the stress is relaxed. It is presumed that the P shape is changed.

Moreover, since the polymer compound has an oxyalkylene carbonyl group, this also contributes to the transesterification reaction. That is, it is presumed that the P shape can be repeatedly changed only by the combination of the cured product and the polymer compound.
When this member does not contain the above-mentioned polymer compound, there is a curable compound represented by the formula 1 in which the oxyalkylene carbonyl group and the hydroxy group contained in the polymer compound are represented by the mechanism described above. It is possible to infer a similar mechanism by which the effects of the present invention can be obtained by substituting possible oxyalkylene carbonyl groups and hydroxy groups.
Next, each component of this member will be described in detail.

[Cured product]
This member contains a cured product having crystallinity obtained by curing a curable compound represented by the formula 1 described later.
The content of the cured product in the present member is not particularly limited, but is 1 to 99% by mass when the total mass of the member is 100% by mass in that a member having a more excellent effect of the present invention can be obtained. Is preferable, and 20 to 80% by mass is more preferable.
The member may contain one kind of cured product alone or two or more kinds. When the member contains two or more kinds of cured products, the total content thereof is preferably within the above numerical range.

In the present specification, the term "cured product has crystallinity" means that a melting peak is detected by DSC (differential scanning calorimetry) measurement (heating rate 10 ° C./min) in accordance with JIS-K7121: 2012. Means that.
As will be described later, the crystal of the cured product is one of the factors for fixing the change in shape when deformed from the P shape to the T shape and melting by heating to cause the change from the T shape to the P shape. ..

This member can be prepared by separately preparing a cured product, a polymer compound, and a transesterification catalyst, mixing them in a solvent, and then removing the solvent.
Further, in that the Semi-IPN structure is more easily formed, a composition containing a curable compound, a polymer compound and a curing agent, which will be described later, is prepared, and energy is applied to the composition to cure the curable compound. It is preferable to obtain a cured product containing a polymer compound, and then add an ester exchange catalyst to the cured product to obtain a member.

It is preferable to add the transesterification catalyst after the curing reaction of the curable compound because it is easier to suppress the occurrence of unintended side reactions in the curing reaction of the curable compound.
When the cured product and the polymer compound form a Semi-IPN structure, it is presumed that the hydroxy group and the oxyalkylene carbonyl group are more likely to be arranged closer in the cured product, and when a larger shape change is given. It is presumed that the ability to maintain (rewrite) the shape of the

(Curable compound)
The curable compound is a compound represented by the following formula 1.

In formula 1, L ¹ represents a polyoxyalkylene carbonyl group.
The polyoxyalkylene carbonyl group is a divalent group composed of a polymer chain having an oxyalkylene carbonyl group as a repeating unit, and specifically, it is a group represented by the following formula II.

In Formula II, L ² represents an alkylene group which may have a branched structure (may be a branched chain), and the ^{number of carbon atoms of L 2} is not particularly limited, but 1 to 20 are preferable. ~ 10 is more preferable.
Among them, a linear alkylene group having 2 to 10 carbon atoms is more preferable as ^{L 2} in that a member having a more excellent effect of the present invention can be obtained.

The alkylene group of L ² in formula II is preferably the same as the number of carbon atoms in the alkylene group of the polyoxyalkylene group L ² of the polymer compound of Formula 2 to be described later has. If it is equal to the number of carbon atoms in the alkylene group of the polyoxyalkylene group L ² of the polymer compound of Formula 2 to be described later number of carbon atoms in the alkylene group of L ² in the formula II it has, increased compatibility between, member The dispersibility of the polymer compound in the medium is further enhanced. As a result, the transesterification reaction is more likely to proceed more uniformly, and the member has a better effect of the present invention.

Further, in Formula II, n represents a number of 2 or more, and is not particularly limited, but is preferably 2 to 100, more preferably 2 to 50. Further, from the viewpoint that the melting point of the cured product can be easily adjusted to a biological temperature of 35 to 42 ° C., when M ¹ is a tetravalent group (that is, when the curable compound has four branches), n is 10 to 35. Is preferable. When M ¹ is a divalent group, n is preferably 20 or less from the same viewpoint as described above.

As will be described later, the melting point of the cured product is related to the temperature at which the T shape is changed to the P shape. Therefore, when this member is applied to medical instruments, cosmetics, etc., the melting point is 35 to 42 ° C. And, it is preferable because the human body temperature can be used as the driving temperature.

When the curable compound is prepared by ring-opening polymerization of a cyclic ester, the number of n can be adjusted by the charging ratio of the polymerization initiator (for example, polyhydric alcohol) and the monomer (for example, lactone compound). More specifically, the lactone compound may be charged so as to react with a desired n-number of hydroxy groups of the polyhydric alcohol.

The number of n ^{can be determined by 1} H-NMR (Nuclear Magnetic Resonance) measurement of the curable compound. At this time, the NMR measurement of the curable compound shall be performed under the following conditions. Specific spectrum assignments and calculation methods for the number of n other than those shown below are as described in Examples described later.

Measuring device: 300 MHz NMR (manufactured by JEOL Ltd.) or equivalent device Solvent: Deuterated chloroform (CDCl ₃ )
Sample concentration: ~ 10 mg / mL (1 mass / vol%)
Reference substance: Tetramethylsilane (TMS)
Measurement ^{Method: 1} H measured resonance frequency 300MHz

Returning to formula 1, X ¹ is a group having a curable group. In the present 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 the structure thereof.
The ^{group having a curable group of X 1} is not particularly limited, but a group represented by the following formula (III) is preferable.

Wherein III, Z represents a curable group, ^{L 3} represents a single bond or a divalent group. In addition, "*" represents a coupling position.
There is no particular restriction on the divalent group ^{L 3, -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 1 to 10 carbon atoms), a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (2 to 10 carbon atoms is preferable). Is preferable), and combinations thereof and the like can be mentioned. Among them, in that the member has an effect of better present invention is obtained, as the ^{L 3,} a single bond, or, -O -, - C (O ) -, an alkylene group, ^{-NR 20} -, and, A combination of these is preferred.

In Formula III, the curable group of Z means a group involved in the curing reaction. The curable group is not particularly limited, but a group capable of radical polymerization is preferable, and an ethylenically unsaturated group is more preferable, in that a member having a more excellent effect of the present invention can be obtained. The ethylenically unsaturated group is not particularly limited, and examples thereof include a (meth) acryloyl group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable.
In addition, in this specification, "(meth) acryloyl" means either one or both of acryloyl and methacryloyl.

Returning to Formula 1, the p + q valent group of M ^1, when M ¹ is a divalent group, although the form thereof is not particularly limited, has already been described as a divalent group of L ³ of formula III or group is preferred, _{or, * - T 2 -L 2 -T} 2 - * group represented by may be mentioned. Here, * represents a bond position, L ₂ represents a divalent group, T ₂ represents a single bond or a divalent group, and the two T _2s may be the same or different from each other. As _{a preferable form of L 2,} a divalent hydrocarbon group (preferably having 1 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), and is divalent. (Preferably, a heterocyclic group having a 5- to 7-membered ring), and the hydrocarbon group may contain a hetero atom (for example, —O—). Specific examples of L ₂ include butanediol residues such as 1,4-butanediol residues.

When M ¹ is a trivalent or higher valent group, the group is not particularly limited, and examples thereof include groups represented by the following formulas (4a) to (4d).

In formula 4a, L ₃ represents a trivalent group. T ₃ represents a single bond or a divalent group, and the three T _3s may be the same or different from each other.
The L _3, nitrogen atom, a trivalent hydrocarbon group (1-10 carbon atoms are preferred. In addition, the hydrocarbon group may be a well-aliphatic hydrocarbon group with an aromatic hydrocarbon group.), Or, A trivalent heterocyclic group (preferably a 5-membered to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a hetero atom (for example, —O—). Specific examples of L ₃ include glycerol residues, trimethylolpropane residues, phloroglucinol residues, cyclohexanetriol residues and the like.

In formula 4b, L ₄ represents a tetravalent group. T ₄ represents a single bond or a divalent group, and the four T _4s may be the same or different from each other.
As the preferred form of the L _4, 4 monovalent hydrocarbon group (having from 1 to 10 carbon atoms are preferred. In addition, the hydrocarbon group may be a well-aliphatic hydrocarbon group with an aromatic hydrocarbon group.) Tetravalent heterocyclic groups (preferably 5- to 7-membered heterocyclic groups) may be mentioned, and hydrocarbon groups may contain heteroatoms (eg —O—). Specific examples of L ₄ include pentaerythritol residue, ditrimethylolpropane residue and the like.

In formula 4c, L ₅ represents a pentavalent group. T ₅ represents a single bond or a divalent group, and the five T _5s may be the same or different from each other.
As the preferred form of the L _5, 5-valent hydrocarbon group (carbon number 2 to 10 are preferred. In addition, the hydrocarbon group may be a well-aliphatic hydrocarbon group with an aromatic hydrocarbon group.), Or A pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a heteroatom (eg, —O—). Specific examples of L ₅ include arabitol residue, fluoroglucolsideol residue, cyclohexanepentaol residue and the like.

In formula 4d, L ₆ represents a hexavalent group. T ₆ represents a single bond or a divalent group, and the six T _6s may be the same or different from each other.
The preferred form of L ₆ is a hexavalent hydrocarbon group (preferably having 2 to 10 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or. , Hexavalent heterocyclic groups (preferably 6 to 7-membered heterocyclic groups), and hydrocarbon groups may contain heteroatoms (eg —O—). Specific examples of L ₆ include mannitol residue, sorbitol residue, dipentaerythritol residue, hexahydroxybenzene, hexahydroxycyclohexane residue and the like.

In the formulas 4a to 4d, the divalent groups represented by _{T 3} to T ₆ may have the same form as the divalent group of ^{M 1 described above, or may be the same.}
When M ¹ is a group having a valence of 7 or more, a group in which the groups represented by the formulas 4a to 4d are combined can be used.

Returning to Equation 1, p represents an integer of 0 or more, preferably 2 or less, more preferably 1 or less, and even more preferably 0.
Further, q represents an integer of 2 or more, preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less.

In formula 1, R ¹ represents a hydrogen atom or a monovalent substituent having no curable group.
The monovalent substituent having no 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, and R'is a hydrogen atom or a hydrocarbon group (which may be linear, branched, or cyclic). , (Poly) represents an oxyalkylene carbonyl group, and * represents a bond position.
Further, R ¹ is preferably a group having no hydroxy group.

Among them, the curable compound is preferably a compound represented by the following formula 1B in that a member having a more excellent effect of the present invention can be obtained.

In formula 1B, M ^1B is an r-valent group, the form of which is similar to the group represented by ^{M 1 in formula 1 described above, including preferred forms.}
L ^1B represents a polyoxyalkylene carbonyl group, X ^1B represents a group having a curable group, and the form thereof is the same as that of L ¹ and X ¹ in the above-described formula 1, including the preferred form.

The curable compound is preferably a compound represented by the following formula 1C in that a member having a more excellent effect of the present invention can be obtained.

In formula 1C, AL ¹ represents a linear or branched alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but generally 1 or more is preferable, 20 or less is preferable, and 10 or less is more preferable. X ^1C represents a group having a curable group, and its form is the same as that of the group represented by ^{X 1 of the formula 1 described above, including the preferred form.}

In the formula 1C, t represents a number of 2 or more, preferably 100 or less, more preferably 50 or less, further preferably 35 or less, and from the viewpoint that the melting point of the obtained cured product crystal can be easily adjusted to 35 to 42 ° C. t is preferably 10 or more, and preferably 35 or less. The method for adjusting t is the same as that already described as the method for adjusting n in Equation II. When t is 10 to 35, an endothermic peak is observed at 35 to 42 ° C. (living body temperature) in the obtained member in the process of raising the temperature of DSC.

Further, as another preferable form of the curable compound, for example, a compound represented by the following formula 1D is also preferable.

In formula 1D, AL ² represents a linear or branched alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but generally 1 or more is preferable, 20 or less is preferable, and 10 or less is more preferable. X ^1D represents a group having a curable group, and its form is the same as that of the group represented by ^{X 1 of the formula 1 described above, including the preferred form.}

In the formula 1D, w represents a number of 2 or more, preferably 100 or less, more preferably 50 or less, and from the viewpoint that the melting point of the crystal of the cured product obtained by curing the curable compound can be easily adjusted to 35 to 42 ° C. , 20 or less is preferable.

The number average molecular weight of the curable compound is not particularly limited, but is generally preferably 500 to 20000, more preferably 1000 to 10000, and even more preferably 1500 to 5000.
The molecular weight distribution (Mw / Mn) of the curable compound is not particularly limited, but is generally preferably 1.00 to 1.50.
The number average molecular weight and the weight average molecular weight of the curable compound mean values obtained by GPC (Gel Permeation Chromatography) measurement by the method described in Examples described later.

-Method for producing a curable compound The method for producing a curable compound is not particularly limited, but the precursor compound obtained by ring-opening polymerization of a cyclic compound is curable in that a curable compound can be obtained more easily. A method obtained by introducing a group having a group is preferable.

As the cyclic compound, a known cyclic compound can be used, and is not particularly limited, but one that can open the ring by hydrolysis is preferable, and for example, β-propiolactone, β-butyrolactone, β-valerolactone, γ- Butyrolactone, γ-valerolactone, γ-caprilolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoic lactone, 2-methyl-ε- Cyclic esters (lactone compounds) such as caprolactone, 4-methyl-ε-caprolactone, ε-caprilolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and α-methyl-γ-butyrolactone; glycolide, And cyclic diesters such as lactide; and the like.

Among them, the lactone compound or lactide is preferable as the cyclic compound in that the reactivity of the ring-opening polymerization is good, and the lactone compound is more preferable in that the reactivity is higher and the raw material is more easily available. β-propiolactone, β-butyrolactone, β-valerolactone, γ-butyrolactone, γ-valerolactone, γ-caprilolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, More preferably, it is at least one selected from the group consisting of ε-caprolactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, and ε-palmitolactone.

The method of ring-opening polymerization of a cyclic compound to obtain a precursor compound is not particularly limited, and examples thereof include a method of ring-opening polymerization using alcohol as an initiator in the presence of a metal catalyst.

・ ・ Metal catalyst The metal catalyst is not particularly limited, but alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, and fatty acid salts such as antimony, carbonates, sulfates, and phosphates. , Oxides, hydroxides, halides, alcoholates and the like.
More specifically, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannous oxide, tin myristate, tin octylate, tin stearate, tetraphenyltin, tin methoxydo. , Tin ethoxydo, tin butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex, titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, zinc oxide, Examples thereof include compounds such as diethyl zinc, antimony trioxide, antimony trioxide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, and yttrium alkoxide.

The amount of the metal catalyst used is preferably about ^{0.01 × 10 -4} to 100 × 10 ^-4 mol per 1 kg of the cyclic compound in terms of the metal element in the metal catalyst.

-Initiator The initiator is not particularly limited, and examples thereof include monovalent or divalent or higher valent alcohols.

The monohydric alcohol is not particularly limited, and examples thereof include alcohols represented by ^{R IN − OH, in which R IN} contains an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. show.
The aliphatic hydrocarbon group is not particularly limited, and examples thereof include an alkyl group having 1 to 20 carbon atoms.
Examples of the monohydric alcohol 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, and the like. Examples thereof include n-decyl alcohol, n-dodecyl alcohol, hexadecyl alcohol, lauryl alcohol, ethyl lactate, and hexyl lactate.

Examples of dihydric or higher alcohols (polyhydric alcohols) include trimethylolethane, ditrimethylolethane, trimethylolpropane, tetramethylene glycol (1,4-butanediol), ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples thereof include trypentaerythritol, glycerin, diglycerol, and trimethylolmelamine.
The amount of the initiator used is not particularly limited, but is preferably about 0.0001 to 0.04 mol per kg of the cyclic compound.

Ring-opening polymerization Ring-opening polymerization is preferably carried out in an inert gas atmosphere in order to prevent 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.

Introducing a curable group The method for introducing a curable group into the precursor compound obtained by ring-opening polymerization of the cyclic compound is not particularly limited, but for example, the reactivity with respect to the hydroxy group of the precursor compound. The method (a) of reacting a compound having both the above-mentioned substituent and the curable group, and the hydroxy group of the precursor compound are substituted with other functional groups to show reactivity with this substituent. Examples thereof include a method (b) of reacting a compound having both a functional group and a curable group. Among them, the method (a) is preferable in that a curable compound (macromonomer) can be obtained more easily.

The compound to be reacted with the hydroxy group of the precursor compound by the above method (a) is not particularly limited, but for example, when the curable group is a (meth) acryloyl group, chloride (meth) acrylic acid ((meth) acrylic acid ((meth) acrylic acid). ) Acryloyl chloride) and unsaturated acid halogen compounds such as brominated (meth) acrylic acid.
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 10 molar equivalents with respect to the hydroxy group.

[Manufacturing method of cured product]
As described above, this member contains a cured product obtained by curing a curable compound. The method for obtaining this cured product is not particularly limited, but a method for obtaining the cured product by applying energy to the composition containing the curable compound is preferable.

When energy is applied to a composition containing a curable compound to obtain a cured product, the content of the curable compound in the composition is not particularly limited, and depends on the content of the cured product in the obtained member. It may be selected as appropriate.
The content of the curable compound in the composition is generally preferably 5 to 80% by mass. The composition may contain one kind of curable compound alone or two or more kinds. When the composition contains two or more kinds of curable compounds, the total content thereof is preferably within the above numerical range.

In the following, components that may be contained in the composition other than the curable compound will be described. Examples of such a component include a curing agent, a solvent, a polymer compound and the like.

(Hardener)
A curing agent is a compound having a function of acting on a curable compound to cause a curing reaction.
The curing agent is not particularly limited, and known compounds can be used. For example, a heat-curing agent in which curing proceeds by applying heat energy and / or a photo-curing agent in which the reaction proceeds by light irradiation (application of light energy) can be used.

Examples of the thermosetting 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, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, and 1, -Acetophenone compounds such as hydroxycyclohexylphenylketone, benzoin ether, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone; diketone compounds such as methylbenzoylformate; 1-phenyl-1,2- Acyloxime ester compounds such as propandion-2- (O-benzoyl) oxime; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfur compounds such as tetramethylthium and dithiocarbamate; Organic oxides such as benzoyl oxide; azo compounds such as azobisisobutyronitrile; organic sulfonium salt compounds; iodonium salt compounds; phosphonium compounds; and the like.

The content of the curing agent in the composition is preferably 0.001 to 10% by mass with respect to the total mass of the curable compound in the composition. The composition may contain one kind of curing agent alone or two or more kinds. When the composition contains two or more kinds of curing agents, the total content thereof is preferably within the above numerical range.

(solvent)
The composition may contain a solvent. The solvent contained in the composition is not particularly limited, but is a solvent capable of dissolving and / or dispersing a curable compound, a polymer compound described later, and a curing agent, and which is difficult to evaporate during the curing reaction. You just have to select.
For example, when benzoyl peroxide (BPO) is used as the curing agent, the temperature of the curing reaction is about 80 ° C., so a solvent having a boiling point equal to or higher than the temperature of the curing reaction is preferable. When such a solvent is used, the evaporation of the solvent during the curing reaction can be further suppressed, so that a cured product having less air bubbles mixed can be easily obtained. Examples of such a solvent include xylene, butyl acetate, DMF (N, N-dimethylformamide), dimethyl sulfoxide and the like.

On the other hand, when a photocuring agent is used as the curing agent, the temperature of the curing reaction is generally lower than that when a thermosetting agent is used, so that a cured product containing less bubbles can be obtained even if a solvent having a lower boiling point is used. .. As the solvent, for example, dichloromethane, chloroform, acetone and the like can be used.

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 kind of solvent alone or two or more kinds. When the composition contains two or more kinds of solvents, the total content thereof is preferably within the above numerical range.

(Polymer compound)
The composition preferably further contains a polymer compound having a repeating unit consisting of an oxyalkylene carbonyl group and having at least two or more hydroxy groups in the molecule. Polymer compounds do not have curable groups. Therefore, it does not contribute to the curing reaction of the curable compound. However, when the curable compound and the polymer compound are uniformly dispersed in advance and then the curable compound is cured, a Semi-IPN structure is more likely to be formed between the cured product and the polymer compound.

When the composition contains a polymer compound, the content of the polymer compound in the composition is not particularly limited, but generally, the total mass of the composition is generally obtained in that a member having a better effect of the present invention can be obtained. Is 100% by mass, 4 to 30% by mass is preferable. The composition may contain one kind of polymer compound alone or two or more kinds. When the composition contains two or more kinds of polymer compounds, the total content thereof is preferably within the above numerical range.

Since the polymer compound has a repeating unit composed of an oxyalkylene carbonyl group, it has high compatibility with the cured product. Therefore, by incorporating the polymer compound into the composition before curing the curable compound, the semi-IPN structure is more likely to be formed in the obtained member. The semi-IPN structure is presumed to contribute to a more rapid P-shape change.

The content of the polymer compound in the member is not particularly limited, but generally 15 to 50 mass when the total mass of the member is 100% by mass in that a member having a better effect of the present invention can be obtained. % Is preferable. The member may contain one kind of polymer compound alone, or may contain two or more kinds of polymer compounds. When the member contains two or more kinds of polymer compounds, the total content thereof is preferably within the above numerical range.

The compound represented by the following formula 2 is preferable as the polymer compound in that a member having a better effect of the present invention can be obtained.

In the formula 2, L ² represents a polyoxyalkylene carbonyl group, and its form is the same as that of the polyoxyalkylene carbonyl group ^{of L 1} in the above-described formula 1, including the preferred form.
Further, in the formula 2, Y ² represents a group having a hydroxy group. In the present specification, the group having a hydroxy group means the hydroxy group itself or an atomic group having a hydroxy group as a partial structure in the structure thereof.
The ^{group having a hydroxy group of Y 2} is not particularly limited, but a group represented by the following formula (IV) is preferable.

Wherein IV, ^{L 5} represents a single bond or a divalent group. In addition, "*" represents a coupling position.
The ^{divalent group of L 5} is not particularly limited, but is the same ^{as the group described as L 3 in} Formula III, including the preferred form.

In formula 2, R ² represents a hydrogen atom or a monovalent substituent having no hydroxy group. The ^{monovalent substituent of R 2 is the same as that} of the monovalent substituent of R ^{1 in} the formula 1, including the preferred form. R ² has neither a hydroxy group nor a curable group.

n2 represents an integer of 2 or more, m2 represents an integer of 0 or more, when n2 is 2 and m2 is 0, ^{M 2} is a single bond or a divalent group, n2 is 2 and m2 is 1 In the above case and when n2 is 3 or more, M ² represents a group of m2 + n2 valence.
In Equation 2, m2 represents an integer of 0 or more, preferably 2 or less, more preferably 1 or less, and even more preferably 0.
Further, n2 represents an integer of 2 or more, preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less.

When M ² is a divalent or higher (divalent, trivalent, tetravalent, etc.) group, it is the same as M ^{1 of} the formula 1 including a preferable form.

Among them, the polymer compound is preferably a compound represented by the following formula 2B in that a member having a more excellent effect of the present invention can be obtained.

In formula 2B, L ^2B represents a polyoxyalkylene carbonyl group, Y ^2B represents a group having a hydroxy group, n _2B represents an integer of 2 or more, M ^2B represents an n _2B valent group, and there are a plurality of Ls. ^2B and Y ^2B may be the same or different from each other.
In addition, L ^2B , Y ^2B , and M ^{2B in the formula 2B are the same as L 2} , M ² , and Y ² in the formula 2, respectively, including suitable forms.
Further, n _2B represents an integer of 2 or more, preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less.

The polymer compound is preferably a compound represented by the following 2C in that a member having a more excellent effect of the present invention can be obtained.

In formula 2C, AL ³ represents a linear or branched alkylene group, and g represents an integer of 2 or more.
In the formula 2C, ^{the alkylene group of AL 3} includes the same group as the alkylene group of AL ^{1 in} the formula 1C, and the preferred form is also the same.
The g is not particularly limited, but is preferably 2 or more, and more preferably 10 or more. It is preferably 100 or less, more preferably 50 or less, and even more preferably 35 or less.

Further, as another form of the polymer compound, the following compound represented by 2D is preferable.

In formula 2D, AL ⁴ represents a linear or branched alkylene group. Examples of the alkylene group of ^{AL 4 include the same groups as the alkylene group of AL 2 in} the formula 1D, including the preferred form, and the preferred forms are also the same.
h is not particularly limited, but is preferably 2 or more, preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less.

-Method for producing a polymer compound The method for producing a polymer compound is not particularly limited, but a method of ring-opening polymerization of a cyclic compound is preferable in that a polymer compound can be obtained more easily.
As a method for ring-opening polymerization of a cyclic compound, the method for producing a precursor compound described as a method for producing a curable compound can be applied, and the preferred form is also the same.

[Transesterification catalyst]
This member contains a transesterification catalyst. The transesterification catalyst has a function of promoting a transesterification reaction between a hydroxy group and an ester bond of a (poly) oxyalkylene carbonyl group, and known compounds can be used without particular limitation.
The content of the transesterification catalyst in the member is not particularly limited, but is generally preferably 0.001 to 5% by mass with respect to the total mass of the member in that a member having a more excellent effect of the present invention can be obtained. .. The member may contain one type of transesterification catalyst alone, or may contain two or more types. When the member contains two or more kinds of transesterification catalysts, the total content thereof is preferably within the above numerical range.

The transesterification catalyst is preferably not contained in the compositions already described. When the transesterification catalyst is not present in the composition, unintended side reactions are less likely to occur in the curing reaction of the curable compound.
That is, it is preferable that the transesterification catalyst is added to the cured product after applying energy to the composition to cure the curable compound.

As the ester exchange catalyst, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid, and other sulfonic acids; basic compounds such as LiOH, KOH, NaOH, and amines; titanium, zirconium, bismuth, zinc. , And metal compounds containing tin and the like.

More specifically, metal compounds include alkyl titanates such as methyl, ethyl-, propyl-, isopropyl-, butyl-, sec-butyl-, tert-butyl-, and 2-ethylhexyl titanate;
Alkyl zirconate such as ethyl-, propyl-, and butyl zirconate;
Alkyl bismuths such as bismuth (2-ethylhexanoate), bismuth neodecanoate, and bismuth tetramethylheptaneioate;
Examples thereof include dibutyltin dilaurate, tin 2-ethylhexanoate (tin octylate), dioctyltin dineodecanoate, alkyltinate such as dimethyltin dioleate, and the like.

Among them, the transesterification catalyst preferably contains tin in that a member having a more excellent effect of the present invention can be obtained.

[Manufacturing method of parts]
The method for manufacturing the member is not particularly limited, and each of the above components may be mixed and molded. The order of mixing is not particularly limited, but in that a member having a more excellent effect of the present invention can be obtained, energy is applied to the composition already described to obtain a cured product obtained by curing the curable compound. On the other hand, it is preferable to add a transesterification catalyst.
Among them, the method for manufacturing the member preferably has the following steps in that a member having a more excellent effect of the present invention can be obtained.

-Curing step: A step of applying energy to a composition containing a curable compound, a curing agent, and a polymer compound to cure the curable compound, and obtaining a cured product containing the polymer compound.
-Catalyst impregnation step: A step of bringing a cured product into contact with a transesterification catalyst and a solution containing a solvent to obtain a member.

Further, the method for manufacturing the member may have the following steps.
-Drying step: A step of drying a member to remove at least a part of a solvent.

-Curing Step The curing step is a step of applying energy to a composition containing a curable compound, a curing agent, and a polymer compound to cure the composition. The type of energy to be applied may be appropriately selected depending on the type of curing agent, and heating and / or light irradiation is preferable.

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

When energy is applied to the composition and the curable compound is cured, the shape of the cured product is once fixed. After that, the member is manufactured through a catalyst impregnation step and, if necessary, a drying step, and the initial P shape depends on the shape of the cured product at the time of the curing reaction in this step.

-Catalyst impregnation step The catalyst impregnation step is a step of bringing the transesterification catalyst and the solution containing the solvent into contact with the cured product. The method of bringing the solution into contact with the cured product is not particularly limited, and examples thereof include a method of immersing the cured product in the solution.
The solvent used in the solution is preferably one that can dissolve the catalyst and swell the cured product. By incorporating the catalyst into the swollen cured product, a member capable of changing the P shape more quickly can be obtained.
The type of solvent is not particularly limited, but dichloromethane, tetrahydrofuran, acetone, N, N-dimethylformamide and the like can be used.
The temperature and time of immersion may be appropriately selected depending on the size and thickness of the member, and examples thereof include a method of immersing in a solution at 20 to 50 ° C. for 1 minute to 24 hours.

-Drying step The drying step is a step of drying the member to remove at least a part of the solvent contained in the member. The drying method is not particularly limited, and examples thereof include a method of allowing to stand at 20 to 50 ° C. for 1 minute to 24 hours, a method of holding under reduced pressure, and the like. The drying conditions may be appropriately selected depending on the shape and thickness of the member.

The size and shape of this member are not particularly limited. It may be determined as appropriate according to the application. Since the P shape of this member is rewritable, the shape at the time of manufacturing (initial P shape) may be a simpler shape in view of productivity. For example, after manufacturing the present member in the form of a film, the P shape may be changed to a three-dimensional shape having a curved surface or the like as necessary.

This member can change the P shape a plurality of times. Therefore, even when the P shape is to be made into a complicated three-dimensional shape having a curved surface, it is not necessary to form the P shape into the P shape at the time of molding the member. In other words, it is not necessary to prepare a mold having such a complicated shape.
Since this member has the above-mentioned characteristics, it can be applied to a cell culture substrate, a medical device such as a ligation device, and the like. The member can also be used as a base material for an adhesive tape having a base material and an adhesive layer arranged on the base material.

[How to use members]
The method of using this member is not particularly limited, but as described above, this member has a feature that the P shape can be changed a plurality of times. Therefore, by heating the manufactured main member to a temperature at which the transesterification reaction occurs under stress, a member having a changed permanent shape (permanent shape changed member) can be obtained.

The heating temperature at which the transesterification reaction is caused is not particularly limited, and may be appropriately determined according to the type of transesterification catalyst contained in the member and the like.
The heating temperature is preferably 120 to 160 ° C., and the heating time may be appropriately determined according to the shape and size of the member, but is generally 0.5 to 4 hours.

In the first change of the P shape, the member is deformed into a desired shape to generate stress inside the member, and when heated according to the above conditions, the polyoxyalkylene carbonyl group of the cured product and the polymer compound An ester exchange reaction occurs between the oxyalkylene carbonyl group of the oxyalkylene carbonyl group and the hydroxy group of the polymer compound having two or more in the molecule.
This reaction is a phenomenon like the recombination of the crosslinked structure, and the stress is relaxed and the deformation of the member is fixed, so that the P shape is changed and the P shape changed member is obtained.

This member can change the P shape a plurality of times. Even in the second and subsequent changes, a reaction occurs between the hydroxy group in the member and the (poly) oxyalkylene carbonyl group, and the P shape is changed by "recombining the crosslinked structure".
Due to the first change in P shape, the structure has changed due to the recombination of the crosslinked structure between the cured product contained in the original member and the polymer compound, so in the second and subsequent changes , A reaction different from the reaction between the cured product contained in the original member and the polymer compound also occurs.
However, even in the second and subsequent changes in the P shape, it is common that the crosslinked structure is rearranged by the transesterification reaction between the hydroxy group and the (poly) oxyalkylene carbonyl group existing in the member. Therefore, the structure of the "P-shaped modified member" obtained by this reaction is clearly understood even in the second and subsequent changes.

[Cell culture substrate]
The cell culture substrate according to the present invention is a cell culture substrate having the present member as described above. FIG. 1 is a perspective view of a cell culture substrate 100 according to an embodiment of the present invention.
The cell culture base material 100 is made of a film-like member.
The cell culture base material 100 is made of a member, but the cell culture base material according to the present invention may have the present member and may have another structure. For example, a coating layer made of another polymer may be provided on the film-like member. The coating layer may be used, for example, to adjust the adhesion of cells.

Next, an example of how to use the cell culture substrate 100 will be described. FIG. 2 shows a procedure for obtaining a cylindrical cultured cell layer using the present cell culture substrate 100.

First, a film-shaped cell culture substrate 100 is prepared (step S11, a in the figure).
Next, a rod-shaped mold 101 is prepared (step S12, b in the figure).
Next, the cell culture base material 100 is wound around the rod-shaped mold 101 (step S13, c in the figure).

Next, the mixture is heated to Temp (1) while being fixed in a rod-shaped mold and held for a predetermined time (step S14, d in the figure). Temp (1) may be at a temperature at which the transesterification reaction occurs, and is preferably 120 to 160 ° C., for example.
The holding time may be appropriately determined according to the shape and size of the film, but is generally preferably 0.5 to 4 hours.

In step S14, the P shape of the cell culture substrate, which was initially in the form of a film, is rewritten into a cylindrical shape. Then, while the temperature of the cell culture substrate is maintained at Temp (2), the cell culture substrate is opened from a cylindrical shape to a film shape, and the cell culture substrate is cooled to Temp (3) in that state.

This Temp (2) is a temperature equal to or higher than the crystal melting point (specifically, about the terminal temperature of the endothermic peak) obtained by differential scanning calorimetry of the member, and is a temperature lower than Temp (1). The temperature of Temp (2) can be adjusted as appropriate, but in general, 10 ° C. or higher is preferable, 35 ° C. or higher is more preferable, 100 ° C. or lower is preferable, and 60 ° C. or lower is more preferable. The crystals are melted by heating and holding in Temp (2).
At this time, the holding time is not particularly limited, but is generally preferably 0.1 to 60 minutes.

Temp (3) is a temperature equal to or lower than the crystallization temperature obtained by measuring with a differential scanning calorimeter. Temp (3) has a temperature lower than that of Temp (2).
By crystallizing while maintaining the stress, the structure is fixed while the stress remains and the T shape is memorized.
The temperature of Temp (3) can be adjusted as appropriate, but in general, 0 ° C. or higher is preferable, 10 ° C. or higher is more preferable, 60 ° C. or lower is preferable, and 40 ° C. or lower is further preferable.

Next, desired cells are cultured on the surface of the obtained film-shaped cell culture substrate, and a cultured cell layer is formed on the cell culture substrate.

Next, when the obtained cell culture substrate with a cultured cell layer is heated to Temp (2), the shape of the cell culture substrate returns to the P shape, that is, the cylindrical shape. Then, the cultured cell layer formed on the surface circle of the cell culture base material is also deformed accordingly, and as a result, a cylindrical cultured cell layer is obtained.
The cultured cell layer may be formed after heating to Temp (2).

According to this method, even if the cultured cell layer has a complicated shape, the P shape of the cell culture substrate is set to the target shape before culturing, while the shape such as on a flat plate that is easier to culture is formed into the T shape. Then, the culture can be carried out in a T shape. Further, after culturing, by returning to the P shape which is the original target shape of the cell culture base material, a cultured cell layer deformed along the shape can be obtained.
This culture substrate can be used in a technical field that requires the formation of a cultured cell layer having a complicated shape, for example, for culturing human tissue in vitro. In this case, if the cell culture temperature is 37 ° C., for example, Temp (2) may be adjusted to a temperature higher than that so as not to lose the activity of the cells. Temp (2) can be adjusted by adjusting the melting temperature of the crystal of the cured product, the method of which has already been described.

When this cell culture substrate is used, the cells are cultured on a flat substrate that is easy to handle, and once the cultured cell layer is formed, operations such as deforming it into a predetermined annular shape can be easily and surely performed, which is complicated. Even a three-dimensional cultured cell layer having a curved surface can be easily formed.

[Ligature device]
The ligation device is an instrument used to ligate a tumor and a biological ridge such as a polyp to block blood flow or remove the biological ridge.
The ligation device according to the present invention will be described with reference to the drawings. FIG. 3 is a schematic view of the ligation device 200 according to the embodiment of the present invention. The ligation device 200 is made of a film-like member.

Next, an example of how to use the ligature device 200 will be described. FIG. 4 shows a procedure for ligating a living tissue using the main ligation device 200.

First, a film-shaped ligation device is created (step S21, h in the figure). The shape and size of the film are not particularly limited, and may be appropriately determined according to the intended use (ligation site, etc.).

Next, a rod-shaped mold 201 having a diameter corresponding to the diameter of the tissue cross section after ligation is prepared (step S22, i in the figure). The diameter of the cross section of the tissue after ligation is determined in consideration of how much the cross section of the target tissue should be narrowed down to achieve the therapeutic purpose.
Next, the member is wound around the prepared rod-shaped mold (step S23, i in the figure).
Next, the mixture is heated to Temp (1) while being fixed in a rod-shaped mold, held for a predetermined time, and then cooled (step S24, i in the figure). Regarding Temp (1), it is the temperature at which the transesterification reaction occurs, as described above.
In this step, the P shape of the ligation device is rewritten.

Next, the temperature is maintained at Temp (2), the ligation device is opened in a film shape, and the ligation device is cooled to Temp (3) while maintaining the stress (step 25, j in the figure). By this step, the T shape of the ligation device becomes a film shape. The reason why the T shape is formed into a film in this method is that it is easy to handle, and the T shape is not limited to the above.

Next, when the ligating device is applied to the target tissue 202 for ligation and heated to Temp (2), the shape of the ligating device returns to the P shape, and the target tissue 202 is squeezed to a desired diameter and ligated (step 26). , In the figure k).

At this time, if the Temp (2) is in the range of 35 to 42 ° C., the shape changes from the T shape (film shape) to the P shape (spiral shape) simply by arranging the ligation device at the target location. Since it is not necessary to heat the ligation device separately, it is particularly preferable when the ligation device is applied endoscopically.

According to this ligation device, the P shape can be rewritten, so it is not necessary to prepare a mold for manufacturing the ligation device according to the case. Also, when applied to the target tissue, it does not require skill in the thread tying technique unlike the conventional ligation device, so it can be applied more easily, especially when performing ligation under an endoscope. can.

[Laminate]
FIG. 5 is a schematic cross-sectional view of the laminated body according to the embodiment of the present invention. The laminate 300 has a member 301 and an adhesive layer 302 arranged on the member 301.
Since the laminated body 300 has the adhesive layer 302, it can be adhered to the adherend, and further, since it has a shape memory ability, it has a function of applying a desired stress to the adherend.

For example, a member is formed by the method already described, the P shape is rewritten, and then an adhesive layer is formed on the member. Next, the member is deformed into a T shape and attached to the adherend. After that, when the member is heated while it is still attached to the adherend, the shape of the member returns to the P shape (or stress is generated to return). As a result, a desired stress can be applied to the adherend.

A known adhesive can be used for the adhesive layer in the present laminate, and a known method can be used as the method of arranging the adhesive layer. For example, a method of applying an acrylic-based or rubber-based adhesive onto the member can be mentioned.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

(Synthesis Example 1: Synthesis of "4b50PCL")
A tetrabranched 50-mer PCL (polycaprolactone) "4b50PCL" was synthesized according to the following procedure.
First, pentaerythritol (0.34 g, 0.0025 mol) as an initiator was weighed in a round-bottom flask and dried under reduced pressure for 6 hours. Next, ε-caprolactone (52.84 mL, 0.5 mol) and tin octylate (catalytic amount, 15 drops) were added to the round bottom flask under a nitrogen atmosphere. Next, the round-bottom flask was immersed in an oil bath at 120 ° C. while maintaining the nitrogen atmosphere, and the ring-opening polymerization reaction was started. After the reaction for 24 hours, the obtained polymer was dissolved in THF (tetrahydrofuran, 150 mL) and then added dropwise to a mixed solvent of diethyl ether / hexane (1: 1 vol / vol%, 2 L) for reprecipitation. After decantation, it was dried under reduced pressure overnight to obtain 4b50 PCL (recovery rate: ~ 100%).

(Synthesis Example 2: Synthesis of "4b10PCL")
A 4-branched decomer PCL "4b10PCL" was synthesized according to the following procedure.
First, pentaerythritol (1.7366 g, 0.0125 mol) as an initiator was weighed in a round bottom flask and dried under reduced pressure for 6 hours. Next, ε-caprolactone (52.84 mL, 0.5 mol) and tin octylate (catalytic amount, 15 drops) were added to the round bottom flask under a nitrogen atmosphere. Next, the round-bottom flask was immersed in an oil bath at 120 ° C. while maintaining the nitrogen atmosphere, and the ring-opening polymerization reaction was started. After the reaction for 24 hours, the obtained polymer was dissolved in THF (150 mL) and then added dropwise to a mixed solvent of diethyl ether / hexane (1: 1 vol / vol%, 2 L) for reprecipitation. After decantation, it was dried under reduced pressure overnight to obtain 4b10 PCL (recovery rate: ~ 100%).
The number average molecular weight of 4b10PCL obtained from the GPC results was 3800, and Mw / Mn was 1.12.

-GPC measurement conditions Measuring device: "Shodex ™" GPC-101
Detector: Differential Refractive Index (RI) Detector Column used: "Shodex ™" GPC KF-804L (sample) + GPC KF-806L (reference) (8.0 mm ID x 300 cm x 2)
Column temperature: 40 ° C
Eluent: THF (tetrahydrofuran), flow velocity 0.8 mL / min Sample: Dissolve in THF at 0.1 mass% and filter with a 0.45 μm membrane filter Molecular weight standard polymer: Polystyrene (molecular weight = 2550, 5060, 10200, 18500) , 37900), 0.1 mass%

(Synthesis Example 3: Synthesis of "2b20PCL")
A bifurcated 20-mer PCL (2b20PCL) was synthesized according to the following procedure.
First, 1,4-butanediol (1.1 mL, 0.0125 mL) as an initiator was weighed in a round bottom flask and dried under reduced pressure for 6 hours. Next, ε-caprolactone (52.84 mL, 0.5 mol) and tin octylate (catalytic amount, 15 drops) were added to the round bottom flask under a nitrogen atmosphere. Next, the round-bottom flask was immersed in an oil bath at 120 ° C. while maintaining the nitrogen atmosphere, and the ring-opening polymerization reaction was started. After the reaction for 24 hours, the obtained polymer was dissolved in THF (150 mL) and then added dropwise to a mixed solvent of diethyl ether / hexane (1: 1 vol / vol%, 2 L) for reprecipitation. After decantation, it was dried under reduced pressure overnight to obtain 2b20 PCL (recovery rate: ~ 100%).
The number average molecular weight of 2b20PCL obtained from the GPC results was 3600, and Mw / Mn was 1.16.

Further, the obtained "4b10PCL" and "2b20PCL" were subjected to ¹ H-NMR measurement under the following conditions, and the number of repetitions of the oxyalkylene carbonyl group was determined. The spectra are shown in FIGS. 6 (4b10PCL) and 7 (2b20PCL). The symbols a to d attached to each peak in the figure indicate that the peak corresponding to the structural formula of 4b10PCL is assigned to each hydrogen atom of the structural formula shown in FIG. The number of repetitions of the oxyalkylene carbonyl group was determined as the integral value (b / d) of the b peak with respect to the integral value of the d peak.
As a result, 4b10PCL was 10 and 2b20PCL was 18.

-NMR measurement conditions Measuring device: 300 MHz NMR (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform (CDCl ₃ )
Sample concentration: ~ 10 mg / mL (1 mass / vol%)
Reference substance: Tetramethylsilane (TMS)
Measurement ^{Method: 1} H measured resonance frequency 300MHz
Observation spectrum width: 0ppm to 10ppm
Spinning: Off Pulse angle: 90 °
Number of integrations: 8 times Dummy scan: 2 times Measurement temperature: Room temperature (20 to 25 ° C) ° C

(Synthesis Example 4: Synthesis of "4b50PCL-m" Macromonomer)
A tetrabranched 50-mer PCL macromonomer "4b50PCL-m" was synthesized according to the following procedure.
First, 4b50 PCL (40.0 g, 0.0016 mol) was weighed, transferred to a round bottom flask, and dissolved in THF (tetrahydrofuran; 300 mL). After complete dissolution, dehydrated triethylamine (10.2 mL, 0.073 mol) was added and stirred for a while. Next, the round-bottom flask was ice-cooled, acryloyl chloride (5.38 mL, 0.067 mol) was added, and the reaction was started. After reacting for 1 day, it was reprecipitated in methanol. In order to remove impurities, reprecipitation was repeated 3 times to obtain "4b50PCL-m" (recovery rate: -80%).

(Synthesis Example 5: Synthesis of "4b10PCL-m" Macromonomer)
A tetrabranched decameric PCL macromonomer "4b10PCL-m" was synthesized according to the following procedure.
First, 4b10 PCL (51.95 g, 0.011 mol) was weighed, transferred to a round bottom flask and dissolved in THF (300 mL). After complete dissolution, dehydrated triethylamine (27.97 mL, 0.2 mol) was added and stirred for a while. Next, the round-bottom flask was ice-cooled, acryloyl chloride (10.98 mL, 0.135 mol) was added, and the reaction was started. After reacting for 1 day, it was reprecipitated in methanol. In order to remove impurities, reprecipitation was repeated 3 times to obtain "4b10PCL-m" (recovery rate: ~ 94%).

(Synthesis Example 6: Synthesis of "2b20PCL-m" Macromonomer)
A bifurcated decameric PCL macromonomer "2b20PCL-m" was synthesized according to the following procedure.
First, 2b20 PCL (50.58 g, 0.0109 mol) was weighed, transferred to a round bottom flask, and dissolved in THF (300 mL). After complete dissolution, dehydrated triethylamine (13.47 mL, 0.0968 mol) was added and stirred for a while. Next, the round-bottom flask was ice-cooled, acryloyl chloride (5.29 mL, 0.0652 mol) was added, and the reaction was started. After reacting for 1 day, it was reprecipitated in methanol. In order to remove impurities, reprecipitation was repeated 3 times to obtain "2b20PCL-m" (recovery rate: ~ 94%).

[Example 1: Synthesis of member 1]
500 mg of 4b50PCL-m, 200 mg of 2b20PCL, and 10 mg of benzoyl peroxide (2% by mass of 4b50PCL-m) were added to 695 μL of xylene and dissolved by stirring to obtain a solution (composition).
Next, the above solution was dropped onto a glass substrate, sandwiched between the glass substrates via a polytetrafluoroethylene spacer (0.2 mm) for adjusting the film thickness, and fixed with a clip so that the solution did not leak. It was placed in an oven at 80 ° C. This was held for 3 hours or more for thermal polymerization (curing), and then the cured film was peeled off from the glass substrate and swollen in acetone. The film was purified by exchanging acetone several times.
After purification, the film was shrunk in methanol and then dried under reduced pressure overnight to obtain a Semi-IPN film. The film was prepared in a size of (length) 10 cm x (width) 10 cm x (thickness) 0.2 mm, and was cut out to a size of about (length) 6 cm x (width) 5 mm x (thickness) 0.2 mm in the evaluation described later. Used.

Next, tin 2-ethylhexanoate was added to dichloromethane so as to have a concentration of 0.5% by mass / volume, and a transesterification catalyst solution was prepared.
The Semi-IPN film cut out as described above was immersed in the transesterification catalyst solution at room temperature for 30 minutes to impregnate the transesterification catalyst.

Next, the film was taken out from the transesterification catalyst solution, left under atmospheric pressure to remove a part of the solvent, and further dried under reduced pressure to obtain member 1.

[Examples 2 to 5: Synthesis of members 2 to 5]
Members 2 to 5 were prepared in the same manner as in Example 1 except that the type and amount of the curable compound used and the type and amount of the polymer compound used were as shown in Table 1. ..

[Example 6]
The member 6 of Example 6 was prepared in the same manner as in Example 1 except that the polymer compound was not used.

[Comparative Example 1]
Member C1 of Comparative Example 1 was prepared in the same manner as in Example 1 except that it was not immersed in the transesterification catalyst solution.
The formulation of each of the above members is shown in Table 1. The blanks in Table 1 mean that the compound was not used.

[DSC measurement]
The DSC measurement was performed using a differential scanning calorimeter (“X-DSC 7000” manufactured by SII Co., Ltd .; heat flux type).
The samples used are as follows.
-Member 6 of Example 6
-Member C1 of Comparative Example 1
-Member 1 of Example 1
-Member 1 after one transesterification reaction in which member 1 is heated to 140 ° C. and then cooled (referred to as "member 11").
The member 12 is further heated to 140 ° C. and then cooled.
-Member 13 in which the member 12 is further heated to 140 ° C. and then cooled.

After preparation, each sample was immediately subjected to the DSC test under the following measurement conditions.

Measuring container: Aluminum sample pan (φ6.8 mm)
Sample amount / size: The sample amount was about 10 mg, and the sample was cut and used so as to fit in the sample pan.
Gas flow rate: N ₂ atmosphere (50 mL / min)
Starting temperature: 120 ° C
Temperature rise rate: 10 ° C / min
End temperature: -10 ° C
Cooling rate: 10 ° C / min

First, the sample is heated from room temperature to 120 ° C., when it reaches 120 ° C., this time it is cooled to -10 ° C at a rate of -10 ° C / min, and the DSC curve of the cooling process from 120 ° C to -10 ° C is cooled. Obtained as a process.
Next, after the temperature of the sample reaches -10 ° C, the temperature is raised to 120 ° C at a rate of 10 ° C / min, and the DSC measurement curve of the heating process from -10 ° C to 120 ° C is heated. Obtained as.

Table 2 shows the melting temperature and the crystallization temperature read from the obtained DSC curve. The "melting temperature" shown in Table 2 is the melting peak temperature, and the "crystallization temperature" is the crystallization peak temperature. The temperature was calculated to one digit after the decimal point and rounded off. The DSC curves are shown in FIGS. 9 to 14.

[P-shape rewriting test]
Member 1 is shown in FIG. Immediately after preparation, the P shape of the member 1 was "film-like" as shown in FIG. Next, this member 1 was spirally wound around a rod made of polytetrafluoroethylene, and its end was fixed with a clip. The member 1 in that state is shown in FIG.
In this state, the member 1 was placed in an oven at 140 ° C. (Temp (1)) and held for 2 hours. FIG. 17 shows the member 1 in a state where the clip and the rod are removed after being held and cooled to room temperature.

The member 1 of FIG. 17 did not return to the “film shape” as shown in FIG. 15 even when the clip and the rod were removed. This indicates that the P shape of the member 1 has been changed (rewritten) from the "film shape" shown in FIG. 15 to the "spiral shape" shown in FIG.
The fact that this "spiral shape" is not a T shape will be described in "Evaluation of shape memory ability" described later.

Next, the member 1 whose P shape has been changed to "spiral" is sandwiched between polytetrafluoroethylene sheets, and the rod has a diameter of about 2 cm in a direction in which the longitudinal direction of the rod and the longitudinal direction of the member 1 are substantially orthogonal to each other. It was wrapped along and its ends were clipped. The member 1 in that state is shown in FIG. Note that FIG. 18 is an enlarged view, and the actual width of the film is the same as that shown in the figure.

In this state, the member 1 was placed in an oven at 140 ° C. and held for 2 hours. After holding, the clip, the sheet made of polytetrafluoroethylene, and the rod were removed, and the member 1 cooled to room temperature is shown in FIG. Note that FIG. 19 was taken from the thickness direction of the film.

The member 1 in FIG. 19 did not return to the "spiral shape" in FIG. 17 even when the clip or the like was removed. This indicates that the P shape of the member 1 has been changed from the "spiral shape" shown in FIG. 17 to the "ring shape" shown in FIG.

Next, the member 1 whose P shape was changed to "ring shape" was sandwiched between sheets made of polytetrafluoroethylene, and fixed in a state of being folded into an "M shape" along the longitudinal direction of the member 1. The member 1 in that state is shown in FIG. Note that FIG. 20 is an enlarged view in which the direction from the front to the back of the drawing is the longitudinal direction of the folded member 1, and the actual width of the film is the same as that of FIG. In this state, the member 1 was placed in an oven at 140 ° C. and held for 2 hours. The member 1 cooled to room temperature after being held is shown in FIG. FIG. 21 is taken from the thickness direction of the film.

The member 1 of FIG. 21 did not return to the “ring shape” of FIG. 19 even when the clip or the like was removed. This indicates that the P shape of the member 1 has been changed from the "ring shape" shown in FIG. 19 to the "M shape" shown in FIG.
From the above results, it was found that the member 1 can arbitrarily change the P shape a plurality of times.

[Evaluation of shape memory]
Next, the shape memory ability was evaluated. First, the member 1 (FIG. 22) having a "spiral" P shape is heated to 60 ° C. (Temp (2)), stretched, cooled to 20 ° C. (Temp (3)) in that state, and then again. It was returned to room temperature. As a result, the T-shape in which the spiral was stretched was memorized (FIG. 23). Next, when the T-shaped member 1 was placed in an oven at 60 ° C., the shape returned to a spiral P-shape (FIG. 24).

From the above results, it was found that the member 1 has a shape memory ability. It can also be confirmed that when returning from the T shape to the P shape, it does not return to the film shape at the time of creation (for example, as shown in FIG. 15), but returns to the "spiral shape" which is the P shape after rewriting. rice field.

The fact that the shape of the member 1 did not return to the "film shape" as shown in FIG. 15 but returned to the "spiral shape" in FIG. 24 means that the P shape changed from "film shape" to "spiral shape" by the above procedure. Indicates that it has been rewritten. In other words, the "spiral" indicates a rewritten P-shape.

When the above P-shape rewriting test and shape memory evaluation were carried out for members 2 to 5, the same results as for member 1 were obtained.

[Evaluation of member C1 in the comparative example]
The member C1 prepared to have the same shape (film shape) as the member 1 was wound around a rod made of polytetrafluoroethylene, and the end portion thereof was fixed with a clip. In this state, the member C1 was placed in an oven at 140 ° C. and held for 2 hours. After holding, the member C1 was cooled to room temperature and the clip and the rod were removed, and the member C1 remained deformed in a spiral shape like the member 1. Two members C1 in this state were prepared.

Next, one of the spiral members C1 was heated to 60 ° C., stretched, cooled to 20 ° C. in that state, and returned to room temperature again. Next, when the deformed member C1 was placed in an oven at 60 ° C., the shape of the member C1 returned to almost "film-like".
Further, when the other one of the spiral members C1 was placed in an oven at 60 ° C., the shape of the member C1 also returned to almost "film-like".

From the above results, it was found that in the member C1, the change in shape from the film shape to the "spiral shape" was not a change from the P shape to the P shape, but a change from the P shape to the T shape. .. In other words, it was found that the P shape of the member C1 remained "film-like".
This is clear from the fact that when the spiral member C1 was stretched and then reheated, it did not return to the spiral shape but returned to almost the film shape.
Therefore, the member C1 of the comparative example which does not contain a predetermined component did not have the desired effect of the present invention.

[Thermomechanical analysis test]
The conditions for the transesterification reaction occurring in the PCL (polycaprolactone) crosslinked product and the Semi-IPN type crosslinked product were measured by a thermomechanical analyzer (TMA450: TA Instruments Co., Ltd.) according to the following procedure.
TMA (Thermomechanical Analysis) Measurement Method:
1: Cut out the samples of member 1, member 6 and member C1 into strips of 3 cm x 0.4 cm and set them in a jig so that they have a length of 8 mm.
2: A load of 0.01 N is applied to the sample, a predetermined temperature (100 to 150 ° C.) is set, and the temperature is equilibrated.
3: A strain of 30% is applied after temperature equilibration, and then the strain is kept constant.
4: Measure the stress relaxation with respect to the time at that time.

25, 26 and 27 show the results obtained by the thermomechanical analysis test, which are thermomechanical analysis curves of member 1, member 6 and member C1, respectively. The data shown in FIGS. 25, 26, and 27 show stress relaxation behavior with respect to the elapsed time (horizontal axis), where the stress (vertical axis) when 30% strain is applied is 1, and the stress value on the vertical axis decreases. The more stress relaxation is, the greater the stress relaxation).
FIG. 26 shows a large temperature-dependent stress relaxation even in the sample (member 6) containing no polymer compound, which is considered to mean that the transesterification reaction is occurring.
FIG. 25 shows that in the Semi-IPN type sample (member 1) containing the polymer compound, the stress decrease with respect to the elapsed time is remarkable and the stress relaxation is larger than that in FIG. 26 (higher stress in a temperature-dependent manner). (Relaxation) is shown, which is believed to mean that the presence of the polymeric compound promotes the rate and efficiency of the transesterification reaction.
FIG. 27 shows that the sample (member C1) containing no transesterification catalyst does not show large stress relaxation in the temperature range of 100 to 150 ° C., which means that the transesterification reaction has not occurred. It is considered that. The use of a transesterification catalyst is essential for the transesterification reaction to take place.

[Evaluation of self-healing characteristics / recycling characteristics]
experimental method:
1: Cut out the sample of member 1 into pieces with scissors (in pieces).
2: Collect the samples cut out separately and sandwich them with a Teflon sheet.
3: The Teflon sheet is further sandwiched between glass plates, and four points are fastened with clips.
4: Place in an oven at 140 ° C. and hold for 2 hours (pressure heat treatment).

FIG. 28 is a diagram showing a disjointed state of the member 1 (left figure) and a sample after pressure heat treatment (right figure). From this, it can be seen that the member 1 can be imparted not only with a shape memory ability (shape rewriting characteristic) in which the P shape can be easily adjusted, but also with a self-repairing characteristic and a recycling characteristic.

100: Cell culture substrate 101: Mold 200: Ligature device 201: Mold 202: Target tissue 300: Laminated body 301: Member 302: Adhesive layer

Claims (23)

1. A cured product having crystallinity obtained by curing a curable compound represented by the formula 1 and a cured product.
   A member containing a transesterification catalyst.
   

   

   
   (In Formula 1, L ¹ represents a polyoxyalkylene carbonyl group, X ¹ represents a group having a curable group, and R ¹ represents a hydrogen atom or a monovalent substituent having no curable group. Represented, q represents an integer of 2 or more, p represents an integer of 0 or more, and when q is 2 and p is 0, M ¹ represents a single bond or a divalent group, q is 2 and p. When is 1 or more and when q is 3 or more, M ¹ represents a group of p + q valence, and a plurality of R ¹ , L ¹ , and X ¹ may be the same or different, respectively.)
2. The member according to claim 1, further containing a polymer compound having a repeating unit composed of an oxyalkylene carbonyl group and having at least two or more hydroxy groups in the molecule.
3. The member according to claim 1 or 2, which has shape memory ability.
4. The member according to any one of claims 1 to 3, wherein an endothermic peak is observed at 35 to 60 ° C. in the process of raising the temperature of differential scanning calorimetry.
5. The member according to any one of claims 1 to 4, wherein the curable compound is represented by the following formula 1B.
   

   

   
   (In formula 1B, M ^1B is an r-valent group, L ^1B represents a polyoxyalkylene carbonyl group, X ^1B represents a group having a curable group, r represents an integer of 2 or more, and there are a plurality of them. L ^1B and X ^1B may be the same or different from each other.)
6. The member according to any one of claims 1 to 5, wherein the curable compound is represented by the following formula 1C.
   

   

   
   (In Formula 1C, AL ¹ represents a linear or branched alkylene group, X ^1C represents a group having a curable group, and t represents a number from 2 to 100.)
7. The member according to any one of claims 1 to 5, wherein the curable compound is represented by the following formula 1D.
   

   

   
   (In Formula 1D, AL ² represents a linear or branched alkylene group, X ^1D represents a group having a curable group, and w represents a number from 2 to 100.)
8. The member according to any one of claims 1 to 7, wherein the polymer compound is represented by the following formula 2.
   

   

   
   (In Formula 2, L ² represents a polyoxyalkylene carbonyl group, Y ² represents a group having a hydroxy group, R ² represents a hydrogen atom or a monovalent substituent having no hydroxy group, and n2. Represents an integer of 2 or more, m2 represents an integer of 0 or more, and when n2 is 2 and m2 is 0, M ² represents a single bond or a divalent group, n2 is 2 and m2 is 1 or more. When, and when n2 is 3 or more, M ² represents a group of m2 + n2 valence, and a plurality of L ² , R ² , and Y ² may be the same or different, respectively.)
9. The member according to any one of claims 1 to 8, wherein the polymer compound is represented by the formula 2B.
   

   

   
   (In Formula 2B, L ^2B represents a polyoxyalkylene carbonyl group, Y ^2B represents a group having a hydroxy group, n _2B represents an integer of 2 or more, M ² represents a group having an n _2B valence, and there are a plurality of them. L ^2B and Y ^2B may be the same or different, respectively.)
10. The member according to any one of claims 1 to 9, wherein the polymer compound is represented by the formula 2C.
    

    

    
    (In the formula 2C, AL ³ represents a linear or branched alkylene group, and g represents a number from 2 to 100.)
11. The member according to any one of claims 1 to 9, wherein the polymer compound is represented by the formula 2D.
    

    

    
    (In the formula 2D, AL ³ represents a linear or branched alkylene group, and h represents a number of 2 or more.)
12. The member according to any one of claims 1 to 11, wherein the transesterification catalyst contains tin.
13. The method for manufacturing a member according to any one of claims 1 to 12.
    An energy is applied to a composition containing the curable compound, the polymer compound, and a curing agent to cure the curable compound to obtain a cured product containing the polymer compound.
    A method for producing a member, which comprises contacting a solution containing the transesterification catalyst and a solvent with the cured product to obtain a member.
14. A method for manufacturing a permanent shape-changed member, wherein the member according to any one of claims 1 to 12 is heated under stress and transesterified to obtain a permanent shape-changed member.
15. A method of changing the permanent shape of a member, wherein the member according to any one of claims 1 to 12 is heated under stress and transesterified to obtain a permanent shape-changed member.
16. A permanent shape-changed member obtained by heating the member according to any one of claims 1 to 12 under stress and performing a transesterification reaction.
17. A method for manufacturing a changed member having a different permanent shape, wherein the permanent shape changed member according to claim 16 is heated under stress and transesterified to obtain a changed member having a different permanent shape.
18. A method of changing the permanent shape of a member to a different permanent shape, wherein the permanent shape-changed member according to claim 16 is heated under stress and transesterified to obtain a changed member having a different permanent shape.
19. A member that has been changed to a different permanent shape, which is obtained by heating the member whose permanent shape has been changed according to claim 16 under stress and performing a transesterification reaction.
20. The member according to any one of claims 1 to 12, 16 and 19 having a permanent shape is deformed into a temporary shape at a temperature of 100 ° C. or lower under stress, and then the member is formed at a temperature equal to or higher than the crystal melting point of the member and 120 ° C. A method of returning the temporary shape of a member to the permanent shape by heating to a temperature lower than that to return the temporary shape to the permanent shape.
21. A cell culture substrate having the member according to any one of claims 1 to 12, 16 and 19.
22. A ligation device having the member according to any one of claims 1 to 12, 16 and 19.
23. A laminate having the member according to any one of claims 1 to 12, 16 and 19, and an adhesive layer arranged on the member.

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