JP2021046481A - Member and method for manufacturing member - Google Patents

Abstract

To provide a member having a shape-memory ability in 3 or more stages.SOLUTION: The member comprises: a crystalline cured product obtained by curing a composition comprising a polymerizable compound expressed by formula (1); and a crystalline polymeric compound having a repeating unit comprising an oxyalkylene carbonyl group. In formula (1), L1 represents a polyoxyalkylene carbonyl group; X1 represents a group having a polymerizable group; R1 represents a hydrogen atom or a monovalent substituent that does not have the above polymerizable group; 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, M1 represents a single bond or a divalent connecting group, and when q is 2 and p is 1 or more, and when q is 3 or more, M1 represents a connecting group having the valency of p+q, and a plurality of L1 may be identical or different from each other.SELECTED DRAWING: Figure 2

Description

The present invention relates to a member and a method for manufacturing the member.

Aliphatic polyester resins such as polycaprolactone are known to have excellent biodegradability and are being studied. Non-Patent Document 1 describes a temperature-responsive poly (εcaprolactone) film.

Advanced materials, 2012, 24, 273

The film described in Non-Patent Document 1 is excellent in that the shape change between the "Temporary" shape after being deformed and the pre-stored "Permanent" shape is triggered by an external thermal stimulus. It had the characteristics. In other words, the film had two levels of shape memory capability.

However, the present inventors have found that the shape memory ability is a function that can memorize a two-stage shape of a "Temporary" shape and a "Permanent" shape, and there is room for further improvement in the number of memorable shapes. did.

Therefore, it is an object of the present invention to provide a member having a function (hereinafter, also referred to as "shape memory ability of 3 steps or more") in which a shape change of 3 steps or more is induced by a thermal stimulus from the outside. .. Another object of the present invention is to provide a method for manufacturing a member.

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 polymer having a crystallinity obtained by curing a composition containing a polymerizable compound represented by the formula 1 described later and a polymer having a repeating unit composed of an oxyalkylene carbonyl group and having a crystallinity. A member containing a compound.
[2] The member according to [1], wherein the melting peak observed by using differential scanning calorimetry is multimodal.
[3] The composition contains a first polymerizable compound having a q of 2 in the formula 1 and a second polymerizable compound having a q of 3 or more in the formula 1 [1] or [2]. ] The member described in.
[4] The member according to [3], wherein q of the second polymerizable compound is 4.
[5] When the molar ratio of the content of the second polymerizable compound to the total of the content of the first polymerizable compound and the content of the second polymerizable compound in the composition is 0.2 or more. A member according to [3] or [4].
[6] The member according to [2], wherein the peak temperature on the lowest temperature side of the melting peaks is 40 ° C. or lower.
[7] The member according to [2], wherein the peak temperature on the hottest side of the melting peaks is 60 ° C. or lower.
[8] The member according to any one of [1] to [7], wherein the polymerizable group is an ethylenically unsaturated group.
[9] The member according to any one of [1] to [8], wherein the group having a polymerizable group is a group represented by the formula 3 described later.
[10] The member according to any one of [1] to [9], wherein the polyoxyalkylene carbonyl group is a group represented by the formula 2 described later.
[11] The member according to [10], wherein n is 5 to 50.
[12] The member according to [10] or [11], wherein the polymer compound has a repeating unit represented by the formula 5 described later.
[13] The member according to [12], wherein ^{L 2} and L ^{5 are the same group.}
[14] A composition containing a polymerizable compound represented by the formula 1 described later and a polymer compound having a repeating unit composed of an oxyalkylene carbonyl group are mixed to obtain a mixture, and energy is applied to the mixture. A method for producing a member, which comprises applying and curing the composition to obtain the member according to any one of [1] to [13].

According to the present invention, it is possible to provide a member having three or more stages of shape memory ability (hereinafter, also referred to as "having the effect of the present invention"). Further, according to the present invention, a method for manufacturing a member can also be provided.

It is a figure which represented typically the differential scanning calorimetry result of the member 1. It is a schematic diagram for demonstrating the three-step shape memory ability of this member. This is the result of differential scanning calorimetry of member 1. This is the result of differential scanning calorimetry of the comparison member. It is an X-ray diffraction intensity distribution of a member 1. It is the crystallinity calculated from the X-ray diffraction intensity distribution of the member 1. It is an X-ray diffraction intensity distribution of a comparative member. It is the crystallinity calculated from the X-ray diffraction intensity distribution of the comparative member. It is an image of a member 1 (first stage, before deformation). It is an image of a member 1 (second stage, at the time of storage). It is an image of a member 1 (third stage, at the time of storage). It is an image of a member 1 (second stage). It is an image of a member 1 (first stage). It is a differential scanning calorimetry result of various members which changed the molar ratio of 4b10-m and 2b20-m.

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.

In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent includes those having no substituent and those having a substituent to the extent that the effect of the present invention is not impaired. To do. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This is also synonymous with each compound.
Further, in the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. In addition, "(meth) acryloyl" represents both or either of acryloyl and methacryloyl.

[Element]
The member according to the embodiment of the present invention (hereinafter, also referred to as “the present member”) is a cured product having crystallinity obtained by curing a composition containing a polymerizable compound represented by the formula 1 described later (hereinafter, also referred to as “the present member”). It is a member containing a "specific cured product") and a polymer compound having a repeating unit composed of an oxyalkylene carbonyl group and having crystallinity (hereinafter, also referred to as "specific polymer compound").

Although the mechanism by which the present member having the above characteristics has the effect of the present invention is not always clear, the present inventors speculate as follows. The following mechanism is speculative, and even if the problem of the present invention is solved regardless of the following mechanism, it shall be included in the scope of the present invention.

The shape writing ability of the present member having three or more stages will be described with reference to the drawings.
Since this member contains a specific cured product and a specific polymer compound, when the temperature is measured by using differential scanning calorimetry (DSC), the endothermic peak related to the melting of the crystal (hereinafter, also simply referred to as “melting peak”). ) Is observed. FIG. 1 schematically shows the DSC measurement results of the member 1 described later. The solid line is the temperature rising process (described as “heating” in the figure), and the alternate long and short dash line is the cooling process (“cooling” in the figure). It is described as.). In FIG. 1, the vertical axis indicates the amount of endotherm in the negative direction (downward direction). The horizontal axis shows the temperature.

In FIG. 1, the curve (heating process) indicated by “heating” has a peak temperature T_trans1 of the crystal melting peak on the low temperature side and a peak temperature T_trans2 of the crystal melting peak on the high temperature side, and the melting peak of the member is It shows that it is bimodal. Such a curve shows, for example, that the peak temperatures of the melting peak of the crystal of the specific cured product and the melting peak of the crystal of the specific polymer compound are different, and that the melting of the crystal of the specific cured product and / or the crystal of the specific polymer compound It is obtained by having two or more peak temperatures (for example, when the member contains a specific cured product of a different type).

In FIG. 1, the melting peak of the crystal of the member is bimodal, but the melting peak of the member is not limited to the above, and for example, the melting peak of the specific cured product and the melting peak of the specific polymer compound. May be synthesized and appear as one broad peak. When the melting peak is bimodal, it is excellent in that the temperature setting when memorizing the shape is clearer (in other words, it is easier to memorize the shape).

In addition, the member may have three or more melting peaks. In that case, the melting peaks are represented as T_trans1, T_trans2, ..., T_transX (where X is an integer of 3 or more) in order from the low temperature side, and will be described below using the above symbols as appropriate.

The fact that the melting peak is multimodal means that the temperature is raised from 0 to 120 ° C at a heating rate of 10 ° C / min using a differential scanning calorimeter, and then at a rate of 5 ° C / min. It means that there are two or more minimum values (melting peaks) of the heat of fusion curve when the temperature is cooled to 20 ° C. and then raised at a heating rate of 5 ° C./min.
Further, the peak temperature of the melting peak means the temperature of the peak top of the melting calorie curve (calorific value curve of the DSC heating process).

Further, according to the curve (cooling process) shown as “cooling” in FIG. 1, the member has two crystallization temperatures (peak temperature of the exothermic peak) on the low temperature side and the high temperature side, respectively. The member is not limited to the above, and for example, even if the exothermic peak of the crystallization of the specific cured product and the exothermic peak of the crystallization of the specific polymer compound are combined and appear as one broad peak. Good.

Next, FIG. 2 is a schematic diagram for explaining the shape memory ability of the present member in three stages. The member 100 has a three-stage shape memory ability that can change its shape in three stages by an external thermal stimulus.

Initially, the member 100 is a flat plate having a smooth surface shape (shape A: first stage). First, the member 100 stores the shape B (second stage). The method for storing the shape B in the member 100 is not particularly limited, but it is preferable to heat the member 100 to a temperature of T_trans2 or higher described in FIG. 1 and deform the member 100 into the shape B. Since the melting peak of the member 100 is bimodal as described above, it is preferable to heat the member 100 to a temperature of T_trans2 or higher on the higher temperature side to deform it into the shape B, but when the member 100 has three or more melting peaks. (Multimodal), it is sufficient to heat to a temperature equal to or higher than the temperature of the melting peak on the highest temperature side, T_transX, and when the melting peak is broad, each of the specific cured product and the specific polymer compound is individually measured by DSC. The same operation as above may be performed with the temperature of the melting peak on the highest temperature side obtained at that time as T_transX.

The member 100 of shape A heated to a temperature of T_trans2 or higher can be deformed into shape B by applying an external force to process (for example, embossing). The method of deforming the member is not limited to the above, and a known deformation method may be appropriately selected depending on the intended use.
After being deformed at a predetermined temperature, the member 100 is cooled to about the crystallization temperature (for example, "T_cry" in FIG. 1, typically less than the crystallization temperature) while applying an external force, and the shape is fixed. To. After the shape is fixed, even if the external force is removed, the original shape A is not restored, whereby the member 101 of the shape B is obtained (the shape B is stored).

At this time, the cooling temperature may be about T_cry, but if the DSC curve (cooling) is bimodal as shown in FIG. 1, it may be cooled to at least about the crystallization temperature on the high temperature side. On the other hand, according to the method of cooling to about the crystallization temperature on the lowest temperature side, the temperature adjustment becomes easier.

Next, the member 101 of the shape B stores the shape C (third stage). The method for storing the shape C in the member 101 is not particularly limited, but it is reheated to a temperature of T_trans1 or higher and lower than T_trans2 described in FIG. 1, deformed into the shape C, and an external force is applied. It is preferable to fix the shape (memorize the shape) by cooling again to about T_cry while maintaining the shape.

Since the melting peak of the member 100 is bimodal as described above, in order to store the shape C (the shape of the third stage), the temperature is T_trans1 or higher on the low temperature side and the temperature on the high temperature side is high. It may be reheated to a temperature lower than T_trans2. The shape B and the shape C can be stored in the member 100 of the shape A by the above method.

Although the example of the shape memory of three stages has been described above, the present member is not limited to the above, and if X is 3, the shape of four stages can be stored. That is, X + 1 types of shapes can be stored. For example, when there are three or more melting peaks, the temperature of the melting peak on the high temperature side is lower than T_transX, and the temperature is reheated to T_trans (x-1) or higher on the lower temperature side to memorize the shape. Just let me do it.

To return to the memorized shape, it may be reheated to the deformation temperature at which the shape was memorized. For example, when the member 102 having the shape C is heated to a temperature of T_trans1 or more and less than T_trans2, it can be returned to the memorized shape B. Further, when the member 101 having a shape B is heated to a temperature of T_trans1 or higher, the member 100 having a shape A is obtained.

The shape, size, etc. of this member are not particularly limited and can be appropriately determined according to the intended use. Members include a plate, a sheet, a molded body having a planar structure on a film, a molded body having a three-dimensional three-dimensional structure, and a composite thereof.

[Cured product]
This member contains a cured product obtained by curing a composition containing a polymerizable compound represented by the following formula 1. The content of the cured product in the present member is not particularly limited, but is generally preferably 50 to 95% 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 kind of cured product alone, or may contain two or more kinds of the cured product. When the member contains two or more kinds of cured products, the total content thereof is preferably within the above numerical range.

<Composition>
The cured product is obtained by curing a composition containing a polymerizable compound represented by the following formula 1. In the following, each component contained in the above composition will be described in detail.

(Polymerizable compound)
The composition contains a polymerizable compound (macromonomer) represented by the following formula 1.

In formula 1, L ¹ represents a polyoxyalkylene carbonyl group, X ¹ represents a group having a polymerizable group, and R ¹ represents a hydrogen atom or a monovalent substituent having no polymerizable group. , P represents an integer of 0 or more, q represents an integer of 2 or more, and when q is 2 and p is 0, M ¹ represents a single bond or a divalent linking group, q is 2 and p. when there 1 or more, and, when q is 3 or more, M ¹ is represents a p + q valent linking group, or different plurality of L ¹ are each the same.

The ^{polyoxyalkylene carbonyl group of L 1} is not particularly limited, but a group represented by the following formula 2 is preferable.

In the formula 2, L ² represents an alkylene group which may have a branched structure, and the number of carbon atoms is not particularly limited, but 2 to 20 is preferable, and 2 to 10 is more preferable. Among them, a linear alkylene group having 2 to 10 carbon atoms is more preferable in that a member having a more excellent effect of the present invention can be obtained.
Further, n represents a number of 2 or more, and is not particularly limited, but 5 to 50 is preferable.
In addition, * represents the coupling position.

The ^{group having a polymerizable group of X 1} is not particularly limited, but a group represented by the following formula 3 is preferable.

In formula 3, Z represents a polymerizable group and L ³ represents a single bond or a divalent linking group. In addition, "*" represents a coupling position.
The ^{divalent linking group of L 3} is not particularly limited, but is -C (O)-, -C (O) O-, -OC (O)-, -O-, -S-, -NR2- (R2). 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), and an alkenylene group (2 to 10 carbon atoms are preferable). ), And combinations thereof and the like can be mentioned.

In the formula 3, the polymerizable group of Z means a group involved in the polymerization reaction. The polymerizable group is not particularly limited, but a radically polymerizable group 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 the formula 1, M ¹ represents a p + q-valent linking group, and when M ¹ is a divalent linking group, the form thereof is not particularly limited, but the divalent linking group ^{of L 3 in the formula 3 is used.} The groups already described as are preferred.

When M ¹ is a linking group having a valence of 3 or more, 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 (having 1 to 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 heteroatom (eg, −O−). Specific examples of L ₃ include glycerin residue, trimethylolpropane residue, phloroglucinol residue, cyclohexanetriol residue 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-valent hydrocarbon group (having 1-10 carbon is preferred. In addition, the hydrocarbon group may be a well-aliphatic hydrocarbon group with an aromatic hydrocarbon group.) A tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group) is mentioned, and the hydrocarbon group may contain a hetero atom (for example, −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 (having 2 to 10 carbon atoms is preferred. In addition, the hydrocarbon group may be a well-aliphatic hydrocarbon group with an aromatic hydrocarbon group.) Alternatively, a pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a hetero atom (for example, −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.
A 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). Alternatively, a hexavalent heterocyclic group (preferably a 6 to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a hetero atom (for example, −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, specific examples and preferred forms of the divalent groups represented by _{T 3 to} T ₆ may be the same as those of the divalent linking group of ^{L 3 described above.}
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.

In formula 1, R ¹ represents a hydrogen atom or a monovalent substituent having no polymerizable group. The monovalent substituent having no polymerizable group is not particularly limited, and examples thereof include a group represented by ^{* -L 4-R'.}
In the above formula, L ⁴ represents a single bond or a divalent linking group, and R'may be either a hydrogen atom or a hydrocarbon group (linear, branched or cyclic). ), (Poly) oxyalkylene group, * represents the bond position.

-Method for producing a polymerizable compound The method for producing a polymerizable compound is not particularly limited, but it is polymerizable to a precursor compound obtained by ring-opening polymerization of a cyclic compound in that a polymerizable compound can be obtained more easily. A method obtained by introducing a group having a group is preferable.
The precursor compound preferably has two or more hydroxy groups (polyol compound).

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 for obtaining the precursor compound by ring-opening polymerization of the cyclic 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 ethoxide, 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 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.

Examples of the monovalent alcohol is not particularly limited, include alcohols represented by R 2 ^-OH, R ² is an aliphatic hydrocarbon group carbon atoms and optionally 1-20 substituted Represent.
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 tetramethylene glycol, trimethylolethane, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, and diglycerol. , And trimethylolmelamine and the like.
The amount of the initiator used is not particularly limited, but is preferably about 0.0001 to 0.04 mol per 1 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.

Introduction of a polymerizable group The method for introducing a polymerizable group into the precursor compound is not particularly limited, and for example, a polymerizable group, a substituent exhibiting reactivity with the hydroxy group of the precursor compound, and the like. The method (a) of reacting the compound (F1) having the above with the precursor compound, and the functional group which substitutes the hydroxy group of the precursor compound with another functional group and exhibits reactivity with this substituent. And the method (b) of reacting the compound (F2) having a polymerizable group together with the above. Among them, the method (a) is preferable in that a polymerizable compound (macromonomer) can be obtained more easily.

The compound (F1) for reacting with the hydroxy group of the precursor compound in the above method (a) is not particularly limited, but for example, when the polymerizable group is a (meth) acryloyl group, chloride (meth). Examples thereof include acrylic acid and unsaturated acid halogen compounds such as brominated (meth) acrylic acid.
The amount of the compound (F1) 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.

(Preferable form of composition)
In that a member having a more excellent effect of the present invention can be obtained, the composition comprises a first polymerizable compound having a q of 2 in the formula 1 and a second polymerizable compound having a q of 3 or more in the formula 1. Is preferably contained.
When the composition contains the first polymerizable compound and the second polymerizable compound, the crystallinity of the obtained cured product is further improved, and / or the mechanical properties of the obtained member are more likely to be improved. ..

-First polymerizable compound The first polymerizable compound is the same as the polymerizable compound already described except that q in Formula 1 is 2, and the preferred form is also the same. Among them, p is preferably 2 or less, and more preferably 0, in that a member having a more excellent effect of the present invention can be obtained.

-Second polymerizable compound The second polymerizable compound is the same as the polymerizable compound already described except that q in Formula 1 is 3 or more, and the preferred form is also the same. Among them, q is preferably 4 to 10 and more preferably 4 to 6 in that a member having a more excellent effect of the present invention can be obtained. Further, p is preferably 2 or less, and more preferably 0.

The molar ratio of the first polymerizable compound to the second polymerizable compound in the composition is not particularly limited, but it can be added to the composition because the temperature of the melting peak on the low temperature side can be easily controlled near the biological temperature. The molar ratio of the content of the second polymerizable compound to the total (sum) of the content of the first polymerizable compound and the content of the second polymerizable compound is preferably 0.2 or more. The upper limit is not particularly limited, but is preferably 0.8 or less.
When the molar content ratio is 0.2 or more, it is more preferable that the melting peak on the lowest temperature side can be easily adjusted to 40 ° C. or lower and a response can be made at the living body temperature.

(Other ingredients)
The composition may contain components other than the above within the range in which the effects of the present invention are exhibited. The components other than the above are not particularly limited, and examples thereof include a polymerization initiator, a solvent (water, an organic solvent, a mixture thereof, etc.) and the like.

-Polymerization Initiator The polymerization initiator is not particularly limited, and a known thermal polymerization initiator and / or a photopolymerization initiator can be used.
Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide.
Examples of the photopolymerization initiator 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 the like. Acetphenone compounds such as 1-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 −propandione-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 peroxide; azo compounds such as azobisisobutyronitrile; organic sulfonium salt compounds; iodonium salt compounds; phosphonium compounds; and the like.

The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator in the composition is preferably 0.001 to 10% by mass with respect to the total mass of the composition.

The method for curing the composition is not particularly limited, and a known curing method can be used. Above all, it is preferable to apply energy (heating and / or light irradiation) to the composition from the viewpoint that a member can be obtained more easily.

[Polymer compound]
This member contains a polymer compound (specific polymer compound) having a repeating unit (hereinafter, also referred to as “specific unit”) composed of an oxyalkylene carbonyl group. The content of the specific polymer compound in the present member is not particularly limited, but is generally preferably 1 to 50% 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 the specific polymer compound alone, or may contain two or more types. When the member contains two or more kinds of polymer compounds, the total content thereof is preferably within the above numerical range.

In addition, in this specification, a specific polymer compound is a compound which does not have a polymerizable group, and is intended to be a compound different from the cured product of the polymerizable compound which has already been described.

Examples of the specific unit include a unit represented by the following formula 5.

In the formula 2, L ⁵ represents an alkylene group which may have a branched structure, and the number of carbon atoms is not particularly limited, but 2 to 20 is preferable, and 2 to 10 is more preferable. Among them, a linear alkylene group having 2 to 10 carbon atoms is more preferable in that a member having a more excellent effect of the present invention can be obtained.

The alkylene group of L ⁵ is preferably the same group as the alkylene group of ^{L 2 described above.} When L ² and L ⁵ are the same group, better compatibility between the cured product (or the polymerizable compound) and the specific polymer compound can be obtained.

The molecular weight of the specific polymer compound is not particularly limited, but is preferably 2000 to 100,000, more preferably 5,000 to 80,000 in that a member having a more excellent effect of the present invention can be obtained.
In the present specification, the molecular weight means a number average molecular weight in terms of PEG (polyethylene glycol) standard measured by a gel permeation chromatography method.

Although not particularly limited, the specific polymer compound is preferably obtained by ring-opening polymerization of a cyclic compound in that a member having more excellent effects of the present invention can be obtained.

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.
The specific polymer compound may be a ring-opening polymerization of one type of cyclic compound alone, or a copolymerization of two or more types. In that case, the sequence in the specific polymer compound of the unit based on two or more kinds of cyclic compounds may be random or block.

Among them, the specific polymer compound is 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-caprolactone, 4-methyl-ε-caprolactone , Ε-caprilolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and cyclic esters (lactone compounds) such as α-methyl-γ-butyrolactone; glycolides and cyclic diesters such as lactide; etc. Is preferably obtained by ring-opening polymerization.

Among them, the specific polymer compound is preferably a linear polymer obtained by ring-opening polymerization of a cyclic compound in that a member having a more excellent effect of the present invention can be obtained. The specific polymer compound may contain a repeating unit other than the above.

[Other ingredients]
The present member may contain a specific cured product and other components other than the specific polymer compound within the range in which the effects of the present invention are exhibited. Other components include, for example, chemicals; magnetic particles for enabling magnetic field manipulation; gold nanorods for enabling photodrive, and photothermal conversion materials such as titanium nitride; semiconductor particles for imaging; Joule heat. Other (liquid) metal / inorganic materials for driving and modification of mechanical properties; clay minerals (modification of mechanical properties) and the like can be mentioned.

-Drugs The drugs are not particularly limited, but are anticancer agents, immunosuppressants, antibiotics, antirheumatic agents, antithrombotic agents, HMG-CoA reductase inhibitors, ACE inhibitors, angiotensin II receptor antagonists, NO donors, calcium antagonists, antihyperlipidemic agents, anti-inflammatory agents, integrin inhibitors, antiallergic agents, antioxidants, GPIIbIIIa antagonists, retinoids, flavonoids, carotinoids, lipid improvers, DNA synthesis inhibitors, Examples thereof include tyrosine kinase inhibitors, antiplatelet agents, vascular smooth muscle growth inhibitors, angiography agents, interferons, growth factors, and combinations thereof.
The member may contain one kind of the drug alone or may contain two or more kinds together.

[Use of members]
Since this member can store the shape in three stages, it can be applied to medical stent materials, actuators, wearable devices, and the like.

[Manufacturing method of parts]
The method for producing this member is not particularly limited, but it can be produced by mixing the components already described. Among them, in that the member can be produced more easily, as a method for producing the member, a composition containing a polymerizable compound represented by the formula 1 already described and a high-grade unit having a repeating unit composed of an oxyalkylene carbonyl group. A method for producing a member is preferable, in which a molecular compound and a molecular compound are mixed to obtain a mixture, and energy is applied to the mixture to cure the composition to obtain a member.

With the above method, it is easy to obtain a member having a desired shape. That is, by injecting the mixture into a mold or the like and then curing the composition, a member having the cured product and the polymer compound can be obtained. The method for obtaining a cured product and the like have already been described, and the preferred form is also the same.

Hereinafter, the present invention will be described in more detail 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.

[Example 1: Preparation of member 1]
[Synthesis of macromonomer (4b10-m)]
First, pentaerythritol was dried under reduced pressure for 12 hours. Next, ε-caprolactone (114.14 g, manufactured by Tokyo Chemical Industry Co., Ltd.) and pentaerythritol (3.40 g, manufactured by Tokyo Chemical Industry Co., Ltd.) were introduced into a three-necked flask, and the mixture was stirred while blowing nitrogen. .. Next, tin octanoate (1-1.5 g) was added to the mixture, and the obtained mixture was held at 120 ° C. for 24 hours to obtain a precursor compound having four hydroxy groups at the ends. Next, the terminal of the precursor compound was reacted with acryloyl chloride to obtain a macromonomer having an acryloyl group. The degree of polymerization of the branched chain of this macromonomer was 10, and this was named "4b10-m". The above scheme is shown in the following formula.
The structure and molecular weight of this macromonomer were measured and estimated by proton nuclear magnetic resonance spectroscopy and gel permeation chromatography.

[Synthesis of macromonomer (2b20-m)]
"2b20-m" was synthesized based on the following scheme in the same manner as the synthesis of 4b10-m except that tetramethylene glycol (butanediol) was used instead of pentaerythritol.

[Synthesis of member 1]
The following ingredients were mixed and dissolved in xylene to prepare a mixture. Next, the mixture was injected between a pair of glass substrates facing each other via a spacer made of polytetrafluoroethylene, and heated at 80 ° C. for 3 hours to obtain a member 1. The member 1 was washed 5 times with acetone, immersed in methanol, and then dried under reduced pressure (overnight).
<Composition of mixture (solid content)>
・ 4b10-m 0.2g
・ 2b20-m 0.3g
L-PCL (corresponds to a polymer compound, manufactured by Sigma-Aldrich, Mn = 80,000, linear, and has no polymerizable group in the molecule including the end of the molecular chain.) 0. 15g
・ Benzoyl peroxide 0.025g

The theoretical molecular weights of the macromonomer (4b10-m) and the macromonomer (2b20-m) were substantially the same, but the mass ratio of both in the mixture was the same as the molar ratio.

[Comparative Example 1: Synthesis of Comparative Members]
The comparison member was synthesized in the same manner as the method for synthesizing the member 1 except that L-PCL was not used. The composition of the mixture was as follows.
<Composition of mixture (solid content)>
・ 4b10-m 0.15g
・ 2b20-m 0.35g
・ Benzoyl peroxide 0.025g

[Differential scanning calorimetry]
With respect to the member 1 and the comparative member, the heating process (heating) and the cooling process (cooling) were measured using a differential scanning calorimeter (“X-DSC 7000” manufactured by SII Co., Ltd.). The temperature rising (cooling) rate was 5 ° C./min.
FIG. 3 shows the results of differential scanning calorimetry of the member 1. The horizontal axis indicates time, and the vertical axis indicates the amount of endotherm (“Endotherm”) in the negative (downward) direction. Further, in FIG. 3, "heating" indicates a temperature raising process, and "cooling" indicates a cooling process.
According to FIG. 3, it was found that the member 1 was bimodal with melting peaks at 37 ° C (T_trans1) and 51 ° C (T_trans2).
In addition, "4b / 2b = 40 / 60-lPCL" in FIG. 3 indicates that 4b10 / 2b20 / L-PCL has a mass ratio of 0.2 g / 0.3 g / 0.15 g. (The ratio of 4b10 and 2b20 is the same as the molar ratio).

FIG. 4 shows the results of differential scanning calorimetry of the comparison member. The meanings of the vertical axis, the horizontal axis, the annotation, and the like are the same as those in FIG. From the results of FIG. 4, it was found that the comparative member had a single melting peak at 38 ° C. In addition, in FIG. 2, "4b / 2b = 30/70" indicates that 4b10 / 2b20 has a mass ratio (molar ratio) of 0.15 g / 0.35 g.

[X-ray diffraction intensity measurement]
For the member 1 and the comparison member, an X-ray diffractometer (“SmartLab” manufactured by Rigaku) is used to inject X-rays of CuKα to which 45 kV and 200 mA are added, and the diffraction angle 2θ is 5 to 40 degrees. The intensity distribution was measured. At this time, the measurement was started from 25 ° C. and measured every 2 ° C. up to 70 ° C. while changing the temperature at 2 ° C./step.
Specifically, after 25 ° C., the temperature was increased to 28 ° C., and the measurement was performed after holding for 10 minutes.
In addition, the crystallinity was calculated from the area of the diffraction peak, and the horizontal axis was plotted as the measurement temperature.

FIG. 5 shows the X-ray diffraction intensity distribution of the member 1. The horizontal axis represents the diffraction angle 2θ (°), and the vertical axis represents the diffraction intensity. Further, FIG. 6 shows the crystallinity calculated from the diffraction intensity distribution of FIG. The horizontal axis of FIG. 6 shows the measurement temperature, and the vertical axis shows the crystallinity (%).
From the results shown in FIGS. 5 and 6, it was confirmed that the member 1 exhibits a two-step temperature response.

FIG. 7 shows the X-ray diffraction intensity distribution of the comparative member. Further, FIG. 8 shows the crystallinity calculated from the diffraction intensity distribution of FIG. 7. From the results shown in FIGS. 7 and 8, it was confirmed that the comparative member did not show a two-step temperature response.

[Confirmation of shape memory ability]
Member 1 (FIG. 9, first stage, length about 35 mm × width about 6 mm × thickness about 0.2 mm) was heated to 60 ° C. and cooled to 4 ° C. in a deformed state. At this time, the member 1 was in the state shown in FIG. 10 (second stage). Next, the member 1 was heated to 40 ° C., deformed and cooled to 4 ° C. At this time, the member 1 was in the state shown in FIG. 11 (third stage).
After that, when the member 1 was heated to 40 ° C., the member 1 changed from the state shown in FIG. 11 (third stage) to the state shown in FIG. 12 (second stage). Next, when the member 1 in the state shown in FIG. 12 was heated to 60 ° C., the member 1 changed to the state shown in FIG. 13 (first stage).
From the results shown in FIGS. 9 to 13, it was found that the member 1 has three stages of shape memory ability.

The comparative member was heated to a temperature above the melting point, cooled to a temperature below the crystallization temperature while being strained, and then heated to a temperature above the melting point. It had only the ability and did not have the three-stage shape memory ability.

[Adjustment of melting peak on the low temperature side]
Using the same method as for member 1, various members having different molar ratios (mass ratios) of 4b10-m and 2b20-m were prepared, and differential scanning calorimetry was performed. The results are shown in FIG.
In FIG. 14, the horizontal axis indicates the molar ratio (%) of the content of 4b10-m to the total of the content of 4b10-m and the content of 2b20-m in the composition.
The vertical axis corresponds to the melting peak on the low temperature side (corresponding to the data plotted on the 1st (left) axis, "circle") and the enthalpy change (corresponding to the data plotted on the 2nd (right) axis, "triangle"). ) Is shown.
From the results of FIG. 14, when the molar ratio of the content of 4b10-m to the total of the content of 4b10-m and the content of 2b20-m in the composition is 0.2 (20%) or more, the temperature is low. It was found that the melting peak on the side was 40 ° C. or lower. When the melting peak on the low temperature side is 40 ° C. or lower, the shape memory ability can be exhibited at the living body temperature, which is more excellent.

100, 101, 102 members

Claims (14)

A cured product having crystallinity obtained by curing a composition containing a polymerizable compound represented by the formula 1 and a cured product.
A member containing a repeating unit composed of an oxyalkylene carbonyl group and a crystalline polymer compound.

(In Formula 1, L ¹ represents a polyoxyalkylene carbonyl group, X ¹ represents a group having a polymerizable group, and R ¹ represents a hydrogen atom or a monovalent substituent having no polymerizable group. Representing, 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 linking group, and q is 2 and when p is 1 or more, and, when q is 3 or more, M ¹ is represents a p + q valent linking group, or different plurality of L ¹ are each the same.) The member according to claim 1, wherein the melting peak observed by using differential scanning calorimetry is multimodal. The member according to claim 1 or 2, wherein the composition contains a first polymerizable compound having a q of 2 in the formula 1 and a second polymerizable compound having a q of 3 or more in the formula 1. .. The member according to claim 3, wherein q of the second polymerizable compound is 4. Claimed that the molar ratio of the content of the second polymerizable compound to the total content of the first polymerizable compound and the content of the second polymerizable compound in the composition is 0.2 or more. Item 3. The member according to Item 3. The member according to claim 2, wherein the peak temperature on the lowest temperature side of the melting peaks is 40 ° C. or lower. The member according to claim 2, wherein the peak temperature on the hottest side of the melting peaks is 60 ° C. or lower. The member according to any one of claims 1 to 7, wherein the polymerizable group is an ethylenically unsaturated group. The member according to any one of claims 1 to 8, wherein the group having a polymerizable group is a group represented by the formula 3.

(In Formula 3, Z represents a polymerizable group, L ³ represents a single bond or a divalent linking group, and "*" represents a bond position.) The member according to any one of claims 1 to 9, wherein the polyoxyalkylene carbonyl group is a group represented by the formula 2.

(In Equation 2, L ² represents an alkylene group that may have a branched structure, * represents a bond position, and n represents a number of 2 or more.) The member according to claim 10, wherein n is 5 to 50. The member according to claim 10 or 11, wherein the polymer compound has a repeating unit represented by the formula 5.

(In formula 5, L ⁵ represents an alkylene group which may have a branched structure.) The member according to claim 12, wherein L ² and L ^{5 are the same group.} A composition containing a polymerizable compound represented by the formula 1 and a polymer compound having a repeating unit composed of an oxyalkylene carbonyl group are mixed to obtain a mixture, and energy is applied to the mixture to obtain the composition. A method for manufacturing a member, wherein the substance is cured to obtain the member according to any one of claims 1 to 13.

(In Formula 1, L ¹ represents a polyoxyalkylene carbonyl group, X ¹ represents a group having a polymerizable group, and R ¹ represents a hydrogen atom or a monovalent substituent having no polymerizable group. Representing, 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 linking group, and q is 2 and when p is 1 or more, and, when q is 3 or more, M ¹ is represents a p + q valent linking group, or different plurality of L ¹ are each the same.)

Images