JP5641695B2 - Thermoresponsive polymer gel and thermoresponsive polymer gel film - Google Patents

Description

  The present invention relates to a thermoresponsive polymer gel and a thermoresponsive polymer gel film formed into a film, and in particular, the thermal responsiveness in which the degree of swelling changes due to thermal stimulation or the surface water droplet contact angle changes. The present invention relates to a polymer gel and a thermoresponsive polymer gel film.

  In recent years, thermoresponsive polymer gels whose swelling degree, volume, etc. are changed by thermal stimulation have been proposed. For example, Patent Document 1 discloses a functional polymer gel in which fine particles serving as crosslinking points are uniformly dispersed so as to have a sufficient amount of change in swelling degree. Is a novel polymer gel composition that produces a volume change in response to an external stimulus, and includes two kinds of polymer compounds that interact with each other to form a polymer complex and a liquid. One of the molecular compounds forms a three-dimensional cross-linked body, and the other has an ionic functional group, dissolves in the liquid, and is inherent in the three-dimensional cross-linked body. Patent Document 3 discloses a stimulus-responsive polymer gel that changes volume by absorbing and releasing liquid, and a resin composition for fixing a polymer gel for dispersing and fixing the stimulus-responsive polymer gel A resin composition for fixing the polymer gel A polymer gel composition comprising a crosslinkable polymer having a weight average molecular weight of 100,000 or more and a crosslinking agent is disclosed. Patent Document 4 swells by absorbing water. Stimulus-responsive polymer hydrogel that is gelled and changes in swelling degree and volume due to stimulus, and that contains a water-insoluble polymer in a phase-separated structure. A gel is disclosed.

JP 2006-36811 A JP 2006-249258 A JP 2007-146000 A JP 2005-264046 A

  Although the degree of swelling and volume of the conventional thermoresponsive polymer gel change due to thermal stimulation, the rate of change is not always high. In addition, although each said patent document has description that a swelling degree, a volume, etc. change with thermal stimulation, there is no description about the change rate, and it is not suggested. That is, conventionally, no attention has been paid to the speed at which the degree of swelling, volume, and the like change, and no effort has been made to improve the speed.

  In addition, although the degree of swelling and volume of the conventional thermoresponsive polymer gel change due to thermal stimulation, the water droplet contact angle on the gel surface hardly changed or even if it changed, the amount of change was extremely large. It was small. In addition, each said patent document does not describe or suggest at all about the change of the water droplet contact angle of the gel surface by thermal stimulation.

  On the other hand, the polymer gels described in Patent Documents 1 to 3 are all finely divided and dispersed in a liquid. Therefore, for example, the polymer gel is retained unless sealed in the sealing member described in Patent Document 2 or 3 It was impossible. Therefore, the volume change of the polymer gel is restricted by the sealing member, and the polymer gel that has been finely divided and dispersed in the liquid cannot be formed into a film.

  The present invention has been made in view of such a situation, and the thermoresponsive polymer gel and the thermal responsiveness in which the degree of swelling changes at a high speed or the water droplet contact angle on the gel surface changes greatly by thermal stimulation. An object is to provide a polymer gel film.

  In order to achieve the above-mentioned object, first, the present invention is a method in which the mass is reduced from the maximum water content to less than 20% of the maximum water content within 300 seconds by heat stimulation, or the surface before and after the heat stimulation. A water-responsive polymer gel is characterized in that the water droplet contact angle difference is 20 ° or more (Invention 1).

  In the said invention (invention 1), it is preferable that the temperature of the said thermal stimulation is room temperature or more and 100 degrees C or less (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the said thermoresponsive polymer gel contains a 10 mass% or more water | moisture content (invention 3).

  In the said invention (invention 1-3), it is preferable that a rotaxane structure is included (invention 4).

  In the above invention (Invention 4), an inclusion complex can be formed with the polymer having two or more cyclic moieties, and a polymer having a blocking functional group at one end and a polymerizable functional group at the other end. It is obtained by copolymerizing the linear molecule and a thermoresponsive component via the polymerizable functional group of the linear molecule of the polymer crosslinking precursor obtained by mixing the linear molecule. It is preferable to contain a crosslinked polymer (Invention 5).

  In the above invention (Invention 5), the cyclic portion of the polymer is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, or a cyclic polyether, a cyclic polyester and a cyclic polyether. It is preferably at least one selected from the group consisting of amines and cyclic polyamines (Invention 6).

  In the said invention (invention 5 and 6), it is preferable that the said thermoresponsive component is a polymeric compound which has N-isopropylamide group (invention 7).

  Secondly, the present invention provides a thermoresponsive polymer gel film formed by forming the thermoresponsive polymer gel (Inventions 1 to 7) into a film (Invention 8).

  According to the present invention, a thermoresponsive polymer gel and a thermoresponsive polymer gel film in which the degree of swelling changes at a high speed or the water droplet contact angle on the gel surface changes greatly by thermal stimulation can be obtained.

It is a schematic diagram which shows the manufacturing process of the thermoresponsive polymer crosslinked body which concerns on one Embodiment of this invention. It is a schematic diagram which shows the structure of the thermoresponsive polymer crosslinked body which concerns on one Embodiment of this invention. It is a graph which shows the relationship between the temperature of a thermoresponsive polymer gel film, and a swelling rate. It is a graph which shows the relationship between the time of a thermoresponsive polymer gel film, and shrinkage | contraction rate. It is a figure explaining the manufacturing method of the gel-like film of a thermoresponsive polymer crosslinked body (E) in an Example.

Hereinafter, embodiments of the present invention will be described.
The thermoresponsive polymer gel according to the present embodiment is
(1) By heat stimulation, the mass decreases from the maximum water content within 300 seconds to 20% or less of the maximum water content, preferably within 15 seconds to 15% or less, or within 100 seconds to 20% or less. Or,
(2) The surface water droplet contact angle difference before and after thermal stimulation is 20 ° or more, preferably 30 ° or more, and more preferably 40 ° or more.

  Here, the temperature of the thermal stimulation is preferably room temperature or more and 100 ° C. or less, particularly preferably 40 to 100 ° C., and more preferably 60 ° C.

  The characteristic (1) defines the rate of change of the degree of swelling of the thermoresponsive polymer gel. Furthermore, since the degree of swelling changes (decreases), the thermoresponsive polymer gel shrinks by releasing moisture, and the characteristic of (1) defines the shrinkage rate of the thermoresponsive polymer gel. But there is.

  The maximum water-containing state means a state in which the thermoresponsive polymer gel is water-containing at room temperature (preferably 23 ° C.) until it cannot be substantially further water-containing. Specifically, it refers to a state in which a dry thermoresponsive polymer gel is immersed in water at room temperature (preferably 23 ° C.) and the swelling can be determined to be substantially stopped from the swelling speed. For example, in this embodiment, the maximum water-containing state is a state in which the swelling degree is less than 5% in 30 minutes after being immersed in water at room temperature (preferably 23 ° C.).

  Conventionally, a thermoresponsive polymer gel having a high rate of change in swelling degree (shrinkage rate) as in (1) has not been known. Conventionally, even such characteristics have not been noticed, and no attempt has been made to improve the rate of change in swelling degree (shrinkage rate) due to thermal stimulation.

  On the other hand, the characteristic of (2) can indicate the degree of change in hydrophilicity to hydrophobicity of the thermoresponsive polymer gel. For example, in this embodiment, since the water droplet contact angle is increased by applying heat stimulation to the thermoresponsive polymer gel, the water droplet contact angle difference is the water droplet contact before the heat stimulation from the water droplet contact angle after the heat stimulation. Calculated by subtracting the corners. “Before and after thermal stimulation” is appropriately determined depending on the temperature and moisture content to which the thermoresponsive polymer gel responds. And any temperature on the high temperature side is sufficient, and the predetermined water droplet contact angle difference may be satisfied by any of the possible water contents. For example, in this embodiment, the difference in the water droplet contact angle on the surface between 23 ° C. and 60 ° C. for a thermoresponsive polymer gel (preferably a thermoresponsive polymer gel film) with a moisture content of 20% by mass is shown. It is preferable to be in the predetermined range.

  In addition, it cannot be overemphasized that the thermoresponsive polymer gel which concerns on this embodiment may satisfy | fill both the characteristics of said (1) and (2).

  The thermoresponsive polymer gel according to the present embodiment contains a thermoresponsive polymer component and moisture, but the moisture content in the thermoresponsive polymer gel is 10% by mass or more. In particular, it is preferably 15 to 100% by mass, and more preferably 20 to 90% by mass. When the water content in the thermoresponsive polymer gel is 10% by mass or more, the characteristic (2) and other characteristics described later are effectively exhibited.

  A preferable thermoresponsive polymer component contained in the thermoresponsive polymer gel according to the present embodiment is a crosslinked thermoresponsive polymer (E) produced by the method schematically shown in FIG. . Hereinafter, the manufacturing method of a thermoresponsive polymer crosslinked body (E) is demonstrated.

  First, a polymer having two or more cyclic moieties (hereinafter referred to as “polymer (A)”) and a linear molecule having a blocking group at one end and a polymerizable functional group at the other end (hereinafter referred to as “polymer (A)”) (Referred to as “linear molecule (B)”) (see FIG. 1).

  The cyclic portion of the polymer (A) can include the linear molecule (B) and can move on the linear molecule (B) in that state. In the present specification, “cyclic” of the “cyclic portion” means substantially “cyclic”, and if the cyclic portion is movable on the linear molecule (B), the cyclic portion is completely May not be closed, for example, may have a helical structure. Further, the polymer (A) is a multimer having a cyclic molecule having a relatively large molecular weight as a constituent part as described later, and its own molecular weight becomes enormous even if the number of repetitions is small. The polymer (A) is a name used for this purpose for convenience, and includes a polymer having a repeating number of oligomer regions of about 2 to 10 mer.

  The molecules constituting the cyclic part (cyclic molecules) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, or cyclic polyethers, cyclic polyesters, cyclic polyetheramines, cyclic polyamines, cyclo A cyclic molecule such as a fan is preferable, and two or more kinds of these cyclic molecules are mixed in the polymer (A) or the polymer cross-linking precursor (C) described later or the heat-responsive polymer cross-linked product (E) described later. It may be.

  When the cyclic molecule is a cyclodextrin, a polymer chain and / or a substituent that can improve the solubility of the polymer (A) in the linear molecule (B) is introduced into the hydroxyl group of the cyclodextrin. It may be. Examples of such a polymer chain include an oxyethylene chain, an alkyl chain, and an acrylate chain. On the other hand, examples of the substituent include an acetyl group, an alkyl group, a trityl group, a tosyl group, a trimethylsilane group, and a phenyl group.

  Specific examples of the cyclic molecule other than cyclodextrin include crown ether or derivatives thereof, cyclic lactone or derivatives thereof, calixarene or derivatives thereof, azacyclophane or derivatives thereof, thiacyclophane or derivatives thereof, cryptand or derivatives thereof, etc. Is mentioned.

  As the cyclic molecule, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and crown ether are preferable because linear molecules are easy to penetrate in a skewered manner. Α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are particularly preferable because they form a complex.

  The number of cyclic molecules in the polymer (A) is 2 or more, preferably 3 to 50, particularly preferably 3 to 5. By having two or more cyclic molecules, a plurality of linear molecules (B) can thereby be included, and the linear molecules (B) are polymerized by polymerizing the linear molecules (B). A plurality of (co) polymers included in the structural unit are bonded to each other via the polymer (A) to form a crosslinked structure. Three or more cyclic molecules are more preferable because the cross-linked structure becomes dense and the strength can be improved without impairing the stress relaxation property of the obtained thermoresponsive polymer crosslinked product (E).

  The structure of the polymer (A) is preferably a structure in which two or more cyclic molecules are linked by a linking moiety. The raw material compound (linking molecule) serving as the linking moiety is preferably a molecule that does not form or is difficult to form an inclusion complex with a cyclic molecule. By using such a linking molecule, when the polymer (A) is synthesized, the cyclic molecule can be linked without closing the opening of the cyclic molecule.

  Such a linking molecule may be linear or branched, but preferably has a side chain that is somewhat bulky. For example, when the cyclic molecule is α-cyclodextrin, it preferably has a side chain that is bulkier than a methyl group. That is, from the viewpoint of not forming an inclusion complex with the cyclic molecule, preferred linking molecules include polypropylene glycol, polyacrylic acid ester, polydimethylsiloxane, polyisoprene and the like, and among them, polypropylene glycol is particularly preferable.

  The number average molecular weight (Mn) of one linking molecule is preferably 100 to 100,000, and more preferably 500 to 10,000. If the number average molecular weight of the linking molecule is less than 100, the openings of the cyclic molecules of the formed polymer (A) are too close to each other so that it is difficult to form a cross-linked structure and the effect based on the interlock structure is sufficiently exerted. There is a risk that it will not be. On the other hand, if the number average molecular weight of the linking molecule exceeds 100,000, the compatibility with the linear molecule (B) or the like may be deteriorated and it may be difficult to form a crosslinked structure.

  The interlock structure refers to a mechanical coupling structure that uses neither non-covalent bonding nor covalent bonding. The interlock structure of the present embodiment is the main body of each linear molecule of two different polymers having the linear molecule (B) as a structural unit at the opening of at least two cyclic molecules of the polymer (A). Each part (described in detail later) penetrates, and each terminal side of the main body part is protected by a blocking group, so that the main body part cannot be pulled out from the opening (rotaxane structure). The two polymers cannot be separated. Due to the interlock structure, the polymer (A) can move through the opening of the cyclic molecule along the main body portion of the linear molecule (B) of the polymer. Compared with the conventional crosslinked structure by covalent bond, it has a binding property of the same strength as that of the covalently crosslinked structure, although the degree of freedom of the crosslinked part is large.

  The mass average molecular weight (Mw) of the polymer (A) depends on the kind of the cyclic molecule, but is usually preferably 1,000 to 1,000,000, particularly 3,000 to 100,000. It is preferable. When the mass average molecular weight of the polymer (A) is less than 1,000, the number of cyclic molecules is often less than 2, and there is a possibility that an interlock structure cannot be formed. Since the parts are very close to each other, the effect based on the interlock structure may not be sufficiently exhibited. On the other hand, when the mass average molecular weight of the polymer (A) exceeds 1,000,000, the compatibility with the linear molecule (B) or the like may be deteriorated and it may be difficult to form a crosslinked structure.

  The polymer (A) can be synthesized by a conventional method. For example, the polymer (A) is obtained by reacting a cyclic molecule having a functional group with a linking molecule having a reactive group capable of reacting with the functional group of the cyclic molecule at the terminal. Specifically, when synthesizing a polymer (A) in which the cyclic molecule is α-cyclodextrin and the linking molecule is polypropylene glycol, α-cyclodextrin and polypropylene glycol having a reactive group at the terminal are mixed. The polymer (A) can be obtained by adding a catalyst if desired and reacting both.

  As the functional group of the cyclic molecule bonded to the linking molecule, for example, a hydroxyl group, a carboxyl group, an amino group, a thiol group and the like are preferable. As the reactive group at the terminal of the linking molecule, for example, an isocyanate group, an epoxy group, an aziridine Groups etc. are preferred. Examples of the connecting molecule include isocyanate compounds such as xylylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and epoxy compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol glycidyl ether. A compound having an aziridine compound such as N, N-hexamethylene-1,6-bis (1-aziridinecarboxyamide) at the terminal can be used.

  The linear molecule (B) is a linear molecule or substance that is included in the cyclic molecule of the polymer (A) and can be integrated by a mechanical bond rather than a chemical bond such as a covalent bond. And having a blocking group at one end and a polymerizable functional group at the other end. In the present specification, “linear” of “linear molecule” means substantially “linear”. That is, as long as the cyclic molecule of the polymer (A) can move on the linear molecule (B), the linear molecule (B) may have a branched chain.

  As a molecule constituting the portion (main body portion) excluding the blocking group and the polymerizable functional group corresponding to both ends of the linear molecule (B), it penetrates through the opening of the cyclic molecule of the polymer (A). It is sufficient that the molecule has a size that can be obtained. For example, when the cyclic molecule of the polymer (A) is α-cyclodextrin, polyethylene glycol, polytetrahydrofuran, polyethylene, polycaprolactone and the like are preferable, and the linear molecule (B) having a main body portion composed of these is Two or more kinds may be mixed in the polymer cross-linking precursor (C) or the thermoresponsive polymer cross-linked product (E).

  The number average molecular weight (Mn) of the molecules constituting the main part of the linear molecule (B) is preferably 100 to 300,000, particularly preferably 200 to 200,000, and more preferably 300 to Preferably it is 100,000. When the number average molecular weight is less than 100, the amount of movement of the cyclic molecule on the linear molecule (B) becomes small, and the resulting thermoresponsive polymer crosslinked product (E) does not have sufficient flexibility. There is a fear. Moreover, when a number average molecular weight exceeds 300,000, there exists a possibility that the solubility to a solvent may worsen.

  The blocking group is not particularly limited as long as the cyclic molecule of the polymer (A) that includes the linear molecule (B) does not leave and can maintain the form of the inclusion complex. Examples of such groups include bulky groups and ionic groups.

  As the blocking group, for example, dialkylphenyl groups, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, anthracenes and the like are preferable. Or 2 or more types may be mixed in the polymer crosslinked body. As a capping agent that forms a blocking group by binding to one end of the linear molecule (B), for example, dimethylphenyl isocyanate, tritylphenyl isocyanate, 2,4-dinitrofluorobenzene, adamantaneamine and the like are preferably used. .

  The polymerizable functional group is not particularly limited as long as it can copolymerize the linear molecule (B) and the thermoresponsive component (D) described later via the polymerizable functional group. As such a polymerizable functional group, for example, (meth) acryloyl group, vinyl group, epoxy group, acetylene group, oxetanyl group and the like are preferable.

  The linear molecule (B) can be synthesized by a conventional method. For example, a linear molecule having a polymerizable functional group at one end, or a linear molecule having a different polymerizable functional group at both ends, and a capping agent for a blocking group are reacted, and one end is A linear molecule (B) can be obtained by leaving the above-mentioned polymerizable functional group and adding a blocking group to the other end.

  As an example, a linear molecule having a hydroxyl group at one end and a (meth) acryloyl group at the other end and a dialkylphenyl group having an isocyanate group are mixed, and if desired, a catalyst is added and both are reacted. Thus, a linear molecule (B) having a dialkylphenyl group as a blocking group at one end and a (meth) acryloyl group as a polymerizable functional group at the other end is obtained.

  When the polymer (A) and the linear molecule (B) described above are prepared, the polymer (A) and the linear molecule (B) are mixed to form an inclusion complex for all or part of the polymer (A) and the linear molecule (B). A polymer crosslinking precursor (C) is produced. That is, one opening of the cyclic molecule of the polymer (A) is penetrated like a skewer with the linear molecule (B), and at least one of the remaining openings of the cyclic molecule of the polymer (A) A polymer cross-linking precursor having a structure in which two or more linear molecules (B) are included in a plurality of cyclic molecules of the same polymer (A), penetrating by another linear molecule (B) (C) is manufactured (see FIG. 1).

  The polymer cross-linking precursor (C) has a structure in which the above-mentioned inclusion complex is formed, but all the openings of the cyclic molecule of the polymer (A) are in such a state. You don't need to be. That is, in the polymer (A) as a mixture, the structure in which the linear molecule (B) is penetrated in only one of the openings of the cyclic molecule, and further the cyclic molecule of the polymer (A) The opening may have a structure in which the linear molecule (B) is not penetrated in a skewered manner, or the linear molecule (B) as a mixture not included in the polymer (A) May be included.

  The polymer crosslinking precursor (C) as described above is prepared by mixing the polymer (A) and the linear molecule (B) in a solvent, for example, water, aqueous sodium hydroxide, dimethylformamide (DMF) and water. In a mixed solution of methanol and water or the like (for example, by adding the linear molecule (B) to the polymer (A) solution) and stirring the solution. it can. The fact that the polymer crosslinking precursor (C) has been obtained can be judged by an increase in the viscosity of the solution.

  There is no restriction | limiting in particular about the stirring method, It can stir by methods, such as a mechanical stirring process and an ultrasonic treatment, at normal temperature or the temperature controlled appropriately, It is preferable to specifically stir by ultrasonic treatment. The stirring time is preferably performed under conditions of several minutes to 1 hour. Although there is no restriction | limiting in particular about the irradiation conditions of an ultrasonic wave, It is preferable to carry out with a frequency of 20-40 kHz.

  Once the polymer cross-linking precursor (C) is produced as described above, the linear molecule is introduced via the polymerizable functional group of the linear molecule (B) included in the cyclic molecule of the polymer (A). (B) and a thermoresponsive component (D) are copolymerized to obtain a thermoresponsive polymer crosslinked product (E) (see FIG. 1). This thermoresponsive polymer crosslinked product (E) includes a rotaxane structure as an interlock structure.

  As the thermoresponsive component (D), it exhibits the thermal response of (1) or (2) above and is copolymerized with the linear molecule (B) via the polymerizable functional group of the linear molecule (B). Possible monomers, oligomers or polymers are selected.

  Preferred examples of the thermoresponsive component (D) include polymerizable compounds having an N-isopropylamide group. The polymerizable compound may be a monomer, or an oligomer or polymer as long as it has a polymerizable functional group. When the polymerizable compound is a polymer, the mass average molecular weight (Mw) is preferably 1,000,000 or less, particularly preferably 100,000 or less. If the mass average molecular weight (Mw) is too large, the compatibility with other components is poor, resulting in a decrease in polymerizability and film-forming property, and there is a possibility that the stimulus response speed also decreases.

  The polymerizable functional group of the polymerizable compound is not particularly limited as long as it is copolymerizable with the linear molecule (B). Examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, an acetylene group, and an oxetanyl group, and a (meth) acryloyl group in consideration of the speed of polymerization and availability. A vinyl group is particularly preferred.

  Considering the above, N-isopropylacrylamide is most preferable as the thermoresponsive component (D).

  Thermal responsiveness in which water or the like is included in the thermoresponsive polymer crosslinked product (E) using the polymerizable compound having N-isopropylamide group (preferably N-isopropylacrylamide) as the thermoresponsive component (D). The polymer gel satisfies the above characteristics (1) and (2), and also exhibits a characteristic that it changes significantly from transparent or translucent to white by thermal stimulation. At this time, the difference in total light transmittance before and after thermal stimulation is preferably 50% or more, and particularly preferably 70% or more.

An example of the thermoresponsive polymer crosslinked body (E) using N-isopropylacrylamide as the thermoresponsive component (D) is schematically shown in FIG. However, the thermoresponsive polymer gel of the present invention is not limited to the embodiment of FIG. In the thermoresponsive polymer crosslinked product (E) shown in FIG. 2, a polymer BD ₁ obtained by copolymerizing a linear molecule (B) and N-isopropylacrylamide which is a thermoresponsive component (D), It is composed of BD ₂ and polymer A _X in which two or more cyclic molecules are bonded by a linking molecule. Then, _{B X} and _{B Y} derived from a linear molecule of the polymer _BD 1, _{BD 2} (B) are each polymer _{A X} through the opening of separate cyclic molecule, and the _{B X} and _{B Y} It has a structure (interlock structure) that cannot be removed by a blocking group present at the end. Incidentally, FIG. 2 in the heat-responsive component (D) has been shown in a state of being incorporated into the main chain of the polymer _BD 1, BD _2, may be present in the side chain of the polymer _BD 1, BD _2, it may be present in the polymer a _X.

  The polymerization reaction may be performed by a conventional method, and is usually performed by radical polymerization. For example, if desired, a photopolymerization initiator is added to the solution containing the polymer crosslinking precursor (C) and the thermoresponsive component (D) and irradiated with ultraviolet rays, or a thermal polymerization initiator is added. When heated, the linear molecule (B) and the thermoresponsive component (D) are copolymerized.

  The photopolymerization initiator is not particularly limited as long as it is usually used, for example, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, Methyl benzoin benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, β- Chloranthraquinone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, (2,4,6-trimethylbenzyldiphenyl) Le) phosphine oxide, 2-benzothiazole -N, it can be used N- diethyldithiocarbamate and the like. In addition, a photoinitiator may be used individually by 1 type and may use 2 or more types together.

The ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, and the irradiation amount is usually 100 to 500 mJ / cm ² .

  On the other hand, the thermal polymerization initiator is not particularly limited as long as it is usually used. For example, benzoyl peroxide, azobisisobutyronitrile (AIBN), or the like can be used. The heating temperature in the case of using the thermal polymerization initiator may be appropriately selected depending on the decomposition temperature of the thermal polymerization initiator, but is usually about 0 to 130 ° C.

  The heat-responsive polymer crosslinked product (E) may be purified by a conventional method, for example, sequentially washed with water, tetrahydrofuran and dimethylformamide.

  According to the above method, the polymer (A) and the linear molecule (B) are simply mixed and stirred without passing through the isolation and purification of the pseudorotaxane, so that the polymer crosslinked precursor (C) can be easily produced. In addition, the obtained polymer cross-linking precursor (C) includes a rotaxane structure having an interlock structure by copolymerizing the linear molecule (B) and the thermoresponsive component (D). The thermoresponsive polymer crosslinked product (E) can be easily produced.

  The obtained thermoresponsive polymer cross-linked product (E) contains, for example, the predetermined amount of water or the like, thereby obtaining a thermoresponsive polymer gel satisfying the above characteristics (1) and / or (2). be able to. In addition, when the obtained thermoresponsive polymer crosslinked product (E) is in the form of a film, the thermal responsiveness satisfying the above characteristics (1) and / or (2) can be obtained by similarly containing water or the like. A polymer gel film can be obtained. This thermoresponsive polymer gel film satisfies the above characteristics (1) and (2), and also exhibits a characteristic that it changes significantly from transparent or translucent to white by thermal stimulation.

  In order to obtain the film of the thermoresponsive polymer gel according to the present embodiment, for example, the polymer cross-linking precursor (C) and the thermoresponsive component (D) are mixed and poured into a mold, A film-like thermoresponsive polymer crosslinked body (E) is formed by coating on a substrate by a to-roll method and then copolymerizing by heating or ultraviolet irradiation, etc., and the resulting film contains moisture You can do it.

  The thickness of a film is 50-5000 micrometers normally, Preferably it is 100-2000 micrometers, Most preferably, it is 150-1500 micrometers.

  The heat-responsive polymer gel and the heat-responsive polymer gel film can be expected to be used in a wide range of fields such as a heat-sensitive sensor, a medical material, a temperature-responsive adhesive, a temperature adjustment film, and a heat-responsive light-shielding film.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
(1) Synthesis of polymer (A) 5 g of α-cyclodextrin (manufactured by Nacalai Tesque) was dissolved in 50 ml of dimethylformamide, and to this solution was added tolylene 2,4-diisocyanate-terminated polypropylene glycol (manufactured by Aldrich, Mn: 1,000). ) 3.4 g and 200 mg of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a tin catalyst, were added and stirred overnight at room temperature.

  The reaction solution is poured into ether and precipitated, and the collected solid is dried, washed with water and dried again, and has α-cyclodextrin as a cyclic molecule and polypropylene glycol as a linking molecule. Thus, 4.6 g of polymer (A) in which 3 to 5 cyclic molecules were connected was obtained.

(2) Synthesis of linear molecule (B) 5 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Mn: 1000) is dissolved in 50 ml of methylene chloride, and 3,5-dimethylphenyl isocyanate (manufactured by Aldrich) is dissolved in this solution. 1.6 g and 200 mg of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a tin catalyst were added and stirred overnight at room temperature.

  Next, 1.7 g of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI) and 100 mg of dibutyltin dilaurate (manufactured by Tokyo Kasei Co., Ltd.) as a tin catalyst were added to the above solution, and the mixture was further stirred overnight at room temperature. .

  The resulting solution was concentrated and then precipitated by pouring into diethyl ether cooled to -75 ° C, and the precipitate was recovered. Accordingly, 3.8 g of polyethylene glycol (MA-PEG-DPI; linear molecule (B)) having a blocking group composed of a 3,5-dimethylphenyl group at one end and a methacryloyl group at the other end. Got.

(3) Production of polymer cross-linking precursor (C) 300 mg of polymer (A) was dissolved in 1 ml of 0.4 wt% sodium hydroxide aqueous solution, and 112 mg of linear molecule (B) was added to this solution mechanically. When ultrasonic irradiation (35 Hz) was performed for 300 seconds with stirring, the solution became cloudy and the viscosity increased. Such a cloudy substance having an increased viscosity is considered to be a polymer crosslinking precursor (C) in which the cyclic molecule of the polymer (A) includes the linear molecule (B).

(4) Production of thermoresponsive polymer crosslinked product (E) To the above-mentioned cloudy substance considered to be a polymer crosslinked precursor (C), 2.0 g of N-isopropylacrylamide is added as a thermoresponsive component (D), and uniform. Stir until. Next, 40 μl of a 1: 1 eutectic mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone (manufactured by Ciba Specialty Chemicals, IRUGACURE 500), which is a photopolymerization initiator, was added, and after deaeration with a vacuum pump Went. Thereafter, as shown in FIG. 5, the mixed solution obtained by the above operation is poured into the silicone rubber mold (thickness 1 mm) on the glass plate, and the glass plate is covered so that air does not enter, A gel-like film was obtained by irradiating ultraviolet rays for 3 minutes (irradiation conditions: illuminance: 3.0 mW / cm ² , light amount: 300 mJ / cm ² ).

  The obtained gel-like film is thermally responsive to the linear molecule (B) via the polymerizable functional group (methacryloyl group) of the linear molecule (B) in the polymer crosslinking precursor (C). Thermally responsive polymer crosslinked product (E) obtained by copolymerization with component (D) (polymer (A) is encapsulated with a polymer side chain having a blocking group at its end, and is thermally responsive. It is considered that the polymer of the component (D) is a thermoresponsive polymer crosslinked product (E)) comprising the polymer main chain.

  The obtained thermoresponsive polymer cross-linked product (E) comprising a gel-like film is taken out by removing the upper glass plate shown in FIG. 5 and washed by sequentially immersing in water, tetrahydrofuran and dimethylformamide. It was dried to obtain a transparent thermoresponsive polymer crosslinked product film (thickness: 1.0 mm, non-stretched).

  Furthermore, a transparent thermoresponsive polymer gel film is obtained by adding moisture to the thermoresponsive polymer crosslinked film at room temperature (23 ° C.) so that the moisture content is 20% by mass. Obtained.

[Comparative Example 1]
Except for using 44 mg of polyethylene glycol diacrylate (corresponding to a crosslinking agent) in place of the polymer (A) in Example 1, a thermoresponsive polymer crosslinked film (thickness: 1.0 mm, Non-stretched). Furthermore, a transparent thermoresponsive polymer gel film is obtained by adding moisture to the thermoresponsive polymer crosslinked film at room temperature (23 ° C.) so that the moisture content is 20% by mass. Obtained.

[Test Example 1] (Measurement of swelling rate)
The thermoresponsive polymer gel films obtained in the examples and comparative examples were immersed in water, and it was confirmed that the change in the degree of swelling in 30 minutes was 5% or less. The temperature was raised from room temperature to 50 ° C. in min. At that time, the mass of the thermoresponsive polymer crosslinked film at each temperature was measured, and the swelling rate was calculated.

The swelling ratio was determined from the difference between the mass of the dried film (W _dry ) and the mass of the film after swelling (W _swell ). The calculation formula is as follows.
Swelling ratio _{[%] = {(W swell} -W dry) / W dry} × 100
The relationship between the temperature thus obtained and the swelling rate is shown in the graph of FIG.

  From the graph of FIG. 3, the thermoresponsive polymer gel film of the example changes from a state where the swelling rate is 1500% at room temperature (23 ° C.) to a swelling rate of 20% or less when the temperature reaches 40 ° C. I understand. On the other hand, the heat-responsive polymer gel film of the comparative example has a swelling rate exceeding 600% at room temperature (23 ° C.), while the swelling rate is 300% at 40 ° C. That is, it can be seen that the thermoresponsive polymer gel films of the examples exhibit very large swelling / shrinking behavior depending on the temperature as compared with the comparative example.

[Test Example 2] (Evaluation of shrinkage behavior)
The thermoresponsive polymer gel films (room temperature: 23 ° C.) obtained in the examples and comparative examples were immersed in water at 50 ° C., the swelling rate S (t) was measured over time, and the shrinkage rate Sn was calculated. did.

The shrinkage rate Sn was obtained by the following formula.
Shrinkage rate Sn = swelling rate S (t) at time (t) / swelling rate S (max) at maximum water content
The relationship between the time thus obtained and the shrinkage rate Sn (shrinkage behavior) is shown in the graph of FIG. The maximum water content state refers to a state in which the change in the degree of swelling when immersed in water at room temperature (23 ° C.) is less than 5% in 30 minutes.

  From the graph of FIG. 4, the thermoresponsive polymer gel film of the example has a significantly faster shrinkage rate to the temperature stimulus than the thermoresponsive polymer gel film of the comparative example, and satisfies the requirements of the present invention. I understand.

[Test Example 3] (Measurement of water droplet contact angle)
A contact angle meter (made by KRUSS, DSA100) was used at a contact angle of 23 ° C. (room temperature) and 60 ° C. (heating) with respect to pure water on the surface of the thermoresponsive polymer crosslinked product film obtained in Examples and Comparative Examples. ). The results are shown in Table 1.

  From Table 1, in the thermoresponsive polymer gel film of the example as compared with the comparative example, the difference in contact angle reached 40 ° or more by heating, and the surface state changed greatly from hydrophilic to hydrophobic. You can see that it meets the requirements.

  The thermoresponsive polymer gel and the thermoresponsive polymer gel film according to the present invention can be expected to be used in a wide range of fields such as a heat-sensitive sensor, a medical material, a temperature-responsive adhesive, a temperature control film, and a heat-responsive light-shielding film. .

Claims (6)

Contains a polymer cross-linker that includes a rotaxane structure in which the opening of the cyclic part is skewered with a linear molecule and a thermoresponsive component bonded to the linear molecule of the rotaxane, and also contains moisture A thermo-responsive polymer gel,
By thermal stimulation, the mass decreases from the maximum water content to less than 20% of the maximum water content within 300 seconds,
A heat-responsive polymer gel characterized in that the water droplet contact angle difference on the surface before and after thermal stimulation is 20 ° or more.   2. The thermoresponsive polymer gel according to claim 1, wherein the temperature of the thermal stimulation is not less than room temperature and not more than 100 ° C. 3.   The thermoresponsive polymer gel according to claim 1, wherein the thermoresponsive polymer gel contains 10% by mass or more of water. A polymer having two or more cyclic moieties, and an opening in the cyclic moiety having a blocking group that does not leave the cyclic moiety that encloses the linear molecule at one end and a polymerizable functional group at the other end Polymerization of the linear molecule of the polymer cross-linking precursor obtained by mixing the polymer and a linear molecule capable of forming a rotaxane structure inclusion complex penetrating the linear part with a linear molecule. Containing a crosslinked polymer obtained by copolymerizing the linear molecule and the thermoresponsive component via a functional group, and containing moisture;
The cyclic portion of the polymer is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, or from the group consisting of cyclic polyether, cyclic polyester, cyclic polyetheramine and cyclic polyamine. At least one selected,
The polymerizable functional group of the linear molecule is a (meth) acryloyl group, a vinyl group, an epoxy group, an acetylene group, or an oxetanyl group,
The thermoresponsive component according to any one of claims 1 to 3, wherein the thermoresponsive component has a functional group capable of being polymerized with a polymerizable functional group of the linear molecule. Molecular gel.   The thermoresponsive polymer gel according to claim 4, wherein the thermoresponsive component is a polymerizable compound having an N-isopropylamide group.   The heat-responsive polymer gel film formed by forming the thermoresponsive polymer gel in any one of Claims 1-5 into a film form.

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