JP2024042777A - Novel photo-decomposable polyrotaxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyrotaxane having high practicality, which can be synthesized easily, to which a photo-decomposable group can be introduced with high efficiency, and a polymer obtained by polymerizing a polymerizable monomer(s) in the presence of which decomposes by radiation of low toxicity UV rays of a relatively high wavelength.

SOLUTION: There is provided polyrotaxane, comprising: cyclic molecules, an axle molecule penetrating through the cyclic molecules, and blocking groups which are positioned on the axial molecule and prevent dethreading of the cyclic molecules, wherein the blocking groups include coumarin derivatives.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a novel polyrotaxane, and more particularly, to a novel polyrotaxane having a cyclic molecule, an axial molecule penetrating the cyclic molecule, and a blocking group disposed on the axial molecule to prevent the cyclic molecule from leaving.

Adhesives are widely used in general industry, medical care, civil engineering, daily life, etc. These adhesives include those that provide adhesiveness through physical bonding force such as cyanoacrylate adhesives, woodworking bonds, and glue, and those that use adhesiveness due to the affinity of surfaces and interfaces such as stickers and tapes. Metal adhesives, ceramic adhesives, dental adhesives, nail adhesives, etc. that provide relatively high adhesive properties through chemical bonds such as van der Waals forces, ionic bonds, hydrogen bonds, and covalent bonds are widely used. ing. A suitable adhesive is selected and used depending on its purpose and use. In particular, adhesives that contain polymerizable monomers, such as cyanoacrylate adhesives that use anionic polymerizable monomers and dental adhesives that use methacrylate polymerizable monomers and polymerization initiators. is preferable because particularly high adhesiveness can be obtained.

Adhesives are widely used everywhere, but they have contradictory properties: if the adhesive strength is too high, it becomes difficult to remove. For example, when an object is glued in the wrong position or state using an adhesive and needs to be re-adhered, or when an object that has been previously glued using an adhesive is removed in order to be recycled. There are cases where you want to separate the objects, or there are cases where you want to remove the hardened adhesive that protrudes from the surface of the object to which the object is adhered when an adhesive is used to adhere the object. In such cases, if the adhesive strength is too high, it may become difficult to remove the object, or if excessive force is applied to force the object to separate, the object itself or the object may become attached. This may result in the destruction of the object. Particularly when the object or object is expensive or rare, or when the object to which the object is attached is biological hard tissue, it is desirable to have a method for detaching the object or object without causing damage to it. It is rare. In particular, adhesives containing polymerizable monomers are widely used in general industry, medical care, civil engineering, daily life, etc. due to their high adhesive properties. Removal from an object or detachment of an object from an object is particularly difficult, and a method for easily detaching it has been desired.

In dental treatments such as caries treatment, treatment in which therapeutic instruments are directly fixed to the tooth surface using adhesives is widely and routinely performed, and adhesives can be said to be the fundamental technology of current dental treatments. Dental adhesives that are expected to be used in dental treatments that require temporary bonding, such as orthodontics, temporary bonding, and temporary fixation, are required to be able to be removed at any time after bonding in these treatments. It is being This technique of attaching and detaching at arbitrary timing is called debonding-on-demand. However, for orthodontic and general dental adhesives, adhesive monomers such as 4-methacryloxyethyl trimellitic anhydride (4-META), which enable stable adhesion to tooth structure, were put into practical use in 1982. Although it has been widely used for 40 years, dental adhesives with a debonding-on-demand function have not been put into practical use, and the technology for attaching and detaching them at any time has not been established in the field of dental bonding. It has not been. Therefore, attachment and detachment of dental materials such as orthodontic brackets bonded to teeth is performed by mechanically peeling off the dental materials or by destroying the dental materials. In these mechanical peeling and material destruction processes, it is difficult to completely prevent damage to the tooth structure (enamel) during the removal of dental materials.・There is a strong demand for dental adhesives with demand functions. Currently, dental adhesives with compositions that are easily removable have been developed and are used in orthodontic treatment. However, there are limits to optimizing the composition of adhesives that combine strong adhesion and debonding-on-demand functionality, and it is necessary to establish new technologies.

Polyrotaxane is a pseudopolyrotaxane in which an axis molecule (axis) passes through the openings of a plurality of cyclic molecules (rotator) to prevent cyclic molecules from being released at both ends of the pseudopolyrotaxane (both ends of the axis molecule). It is made by arranging a blocking group. For example, polyrotaxane (hereinafter, cyclodextrin may be simply abbreviated as "CD") as the cyclic molecule and polyethylene glycol (hereinafter, may be abbreviated as "PEG") as the axial molecule. Patent Document 1) has various characteristics and has been actively researched in recent years.

A polyrotaxane in which an axial molecule penetrates through the openings of at least two cyclic molecules, the cyclic molecule has a reactive group, and a blocking group is present at both ends of the axial molecule; A pressure-sensitive adhesive composition is known that is characterized by containing a pressure-sensitive adhesive polymer having two or more reactive functional groups (Patent Document 2). A hydroxyl group, a carboxyl group, or an amine group is used as the reactive group, and the adhesive sheet has an adhesive layer that has excellent flexibility, a high gel fraction, and is durable, and the adhesive that constitutes the adhesive layer. A pharmaceutical composition is provided.

An adhesive composition that easily achieves the removal of the adhesive layer from the object and the detachment of the object adhered to the object includes (A) a polymerizable monomer, (B) a cyclic molecule, and the cyclic molecule. It has an axial molecule penetrating the molecule, and a blocking group placed on the axial molecule to prevent the cyclic molecule from detaching, and a degradable group is introduced into at least one of the cyclic molecule or the axial molecule, and Adhesive compositions containing polyrotaxanes are known in which the decomposable group causes ring-opening of a cyclic molecule or cleavage of an axial molecule by decomposition (Patent Document 3). Patent Document 3 discloses the use of a photodegradable polyrotaxane having a nitrobenzyl group introduced at the end of the shaft molecule as a dental adhesive. In the adhesive component crosslinked via photodegradable polyrotaxane, the tensile strength decreased because the crosslinked structure collapsed as the polyrotaxane decomposed due to light irradiation, and the adhesive strength decreased significantly due to ultraviolet light irradiation.

The invention also includes a plurality of cyclic molecules and one linear polymer having a terminal group, and the linear polymer includes at least two linear polymer moieties connected via at least one degradable moiety. It is known that polyrotaxane compounds are used as dental adhesives (Patent Document 4). A photodegradable polyrotaxane in which polymerizable functional groups are introduced into multiple cyclodextrins (CDs) acts as a crosslinking agent, so it is possible to easily create a three-dimensional structure by copolymerizing with other monomers. Furthermore, the three-dimensional structure can be decomposed by ultraviolet irradiation, reducing its mechanical strength. For example, if such a photodegradable polyrotaxane crosslinking agent is used as a resin monomer in dental materials, it can be cured by visible light irradiation. However, it is known that it can be developed into a dental adhesive that decomposes upon irradiation with ultraviolet light (Patent Document 4). Patent Document 4 discloses the use of a photodegradable polyrotaxane in which a nitrobenzyl group that is cleaved by ultraviolet light is introduced into the center of the axial molecule as a dental adhesive.

Another technique for easily removing the adhesive layer from the object or detaching the object from the object is to use a material (non-containing material) in which a bond that is broken by heating is introduced into the crosslinking component of the adhesive. Patent Document 1) and a technique for reducing adhesion between metals by applying an electric current (Non-Patent Document 2) are known. Furthermore, adhesives with debonding-on-demand functionality are currently being actively researched for application in a variety of fields, not just dentistry, and their physical properties change mainly due to external stimuli. materials are used (Non-Patent Document 3).

Japanese Patent Application Laid-Open No. 06-025307 Japanese Patent Application Publication No. 2007-224133 JP2016-89175A International Publication No. 2017/191827

Alexander M. Schenzel, et al. Adv Sci (Weinh). Mar; 3(3): 1500361 (2016) N. Kajimoto et al. Dent. Mater. J. 37, 768 (2018) Chem. Sci. 2021, 12, 15183

However, the technology in Non-Patent Document 1 requires heating at 80 to 100°C, and the technology in Non-Patent Document 2 is limited to adhesion between metals, requires the application of electric current, and uses an ionic liquid as a component. Both are toxic and are of poor practical use. Current dental treatment does not apply heat or electric current, so equipment will need to be developed for practical use. In addition, the polyrotaxane in which a nitrobenzyl group is introduced at the end of the shaft molecule described in Patent Document 3, and the polyrotaxane in which a nitrobenzyl group is introduced in the center of the shaft molecule described in Patent Document 4, have a nitrobenzyl group that is a photodegradable group. There are problems such as the fact that only about 70 to 90% of these substances can be introduced and the synthesis is incomplete, and that they decompose at a low wavelength of 250 nm, so the depth of light reaching is shallow and there are concerns about phototoxicity. The polymer obtained by polymerizing a polymerizable monomer in the presence of polyrotaxane has problems such as not being completely decomposed even when irradiated with ultraviolet light because the decomposed product exhibits a large molar extinction coefficient. . Furthermore, the polyrotaxane described in Patent Document 3 in which a nitrobenzyl group is introduced at the end of the shaft molecule requires eight steps to manufacture, and the polyrotaxane described in Patent Document 4 in which a nitrobenzyl group is introduced in the center of the shaft molecule. The production required five steps, and all of them were time-consuming.

Therefore, the present invention can be easily synthesized, a photodegradable group can be introduced with high efficiency, and the polymer obtained by polymerizing a polymerizable monomer in the presence of the photodegradable group has a relatively high wavelength. The purpose of the present invention is to provide a highly practical polyrotaxane that is decomposed by ultraviolet light irradiation with low toxicity.

After intensive study, the present inventors found that a polyrotaxane containing a coumarin derivative as a blocking group, which can be easily synthesized, can introduce a photodegradable group with high efficiency, and can be used at relatively high wavelengths. The polymer obtained by polymerizing the polymerizable monomer in the presence of this decomposes when irradiated with low-toxicity ultraviolet light at a relatively high wavelength such as about 360 nm. It was discovered that it can be decomposed and has excellent practicality.

That is, in a first aspect, the present invention provides a polyrotaxane having a cyclic molecule, an axial molecule penetrating the cyclic molecule, and a blocking group arranged on the axial molecule to prevent detachment of the cyclic molecule. , the blocking group comprises a coumarin derivative.

Further, in a second aspect, the present invention provides an adhesive composition containing the polyrotaxane described in the first aspect and a polymerizable monomer.

Further, in a third aspect, the present invention provides the adhesive composition according to the second aspect, which is used for biological hard tissue.

Further, in a fourth aspect, the present invention provides the adhesive composition according to the third aspect, which is used for dentistry.

In addition, in a fifth aspect, the present invention provides an adhesive composition according to the fourth aspect, which is used for bonding orthodontic brackets or for temporarily attaching implants.

Further, in a sixth aspect, the present invention provides an adhesive comprising the adhesive composition according to any one of the second to fifth aspects.

In a seventh aspect, the present invention provides a method for reducing the mechanical strength of a cured product of the adhesive composition according to any one of the second to fifth aspects, the method comprising the step of irradiating the cured product with ultraviolet light.

The novel polyrotaxane provided by the present invention can be easily synthesized, photodegradable groups can be introduced with high efficiency, and it can be decomposed by irradiation with relatively high wavelength, low toxicity ultraviolet light. The polymer obtained by polymerizing the polymerizable monomer in the presence of this polymer is decomposed by irradiation with relatively high wavelength and low toxicity ultraviolet light, so it has excellent practicality. The reason why these decompose upon irradiation with ultraviolet light is that the coumarin derivative, which is a blocking group that prevents the detachment of the cyclic molecule contained in the polyrotaxane provided by the present invention, decomposes upon irradiation with ultraviolet light, and the axial molecule forms a skewered shape. This is presumed to be due to the fact that the cyclic molecule that has been included in the molecule becomes able to detach from the axial molecule, and the structure of the polyrotaxane provided by the present invention collapses. Since the composition containing the polyrotaxane provided by the present invention and a polymerizable monomer is cured by causing polymerization of the polymerizable monomer in the presence of the polyrotaxane provided by the present invention, the adhesive composition is It can be used as an object. The cured product of the adhesive composition, which is the cured adhesive composition, is decomposed by irradiation with relatively high wavelength and low toxicity ultraviolet light, resulting in a decrease in mechanical strength and adhesive strength. The cured product of the adhesive composition can be detached from the adhered object at any time in a minimally invasive manner. The cured product of the adhesive composition is decomposed by irradiation with relatively high wavelength and low toxicity ultraviolet light, and is highly safe for living organisms, so the adhesive composition can be used for living hard tissues, In particular, it can be used for dental purposes such as bonding of orthodontic brackets or temporary implant attachment. Light irradiation is routinely used for resin effects and whitening in current dental treatment, and can be performed using existing dental equipment as is. It is suitable as

FIG. 1 is a graph showing the light absorption characteristics of the polyrotaxane of the example. FIG. 2 is a graph showing the light absorption characteristics of polyrotaxanes of Examples or Comparative Examples. FIG. 3 is a graph showing the decomposition efficiency of polyrotaxanes of Examples and Comparative Examples when irradiated with visible light or near-ultraviolet light. FIG. 4 is a graph showing the maximum tensile stress (breaking strength) of a cured product obtained by polymerizing a polymerizable monomer in the presence of a polyrotaxane of an example or a reference example.

The present invention provides a polyrotaxane having a cyclic molecule, an axial molecule penetrating the cyclic molecule, and a blocking group arranged on the axial molecule to prevent detachment of the cyclic molecule, wherein the blocking group comprises a coumarin derivative. The present invention provides polyrotaxanes containing polyrotaxanes.

The polyrotaxane of the present invention is a multimer composed of cyclic molecules having a relatively large molecular weight, and even if the number of inclusions (repetition number) of the cyclic molecules present in a state of inclusion in one polyrotaxane molecule is small, has a huge molecular weight. The "polyrotaxane" in the polyrotaxane of the present invention is a convenient name based on this, and includes those with a repeating number of oligomer regions of about 2 to 10 mer.

In the polyrotaxane of the present invention, the cyclic molecule is penetrated by the shaft molecule, and is rotatable and movable around the shaft molecule while being penetrated, and is separated from the shaft molecule by the blocking group arranged on the shaft molecule. Exists in a non-detachable state. In addition, in the polyrotaxane of the present invention, "cyclic" in "cyclic molecule" means substantially "cyclic", and the cyclic molecule does not have to be completely closed, but is substantially free from the axis molecule. For example, it may have a spiral structure as long as it maintains a skewered shape.

As the cyclic molecule, conventionally known cyclic molecules can be used. Examples of such cyclic molecules include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, cyclic polyethers, cyclic polyesters, cyclic polyether amines, cyclic polyamines, and cyclophanes. Can be mentioned.

In one molecule of the polyrotaxane of the present invention, only one type of cyclic molecule may be present in an inclusion state, or two or more types may be present in a mixture.

As cyclic molecules, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and crown ethers are used because they have a relatively large ring diameter and the shaft molecules can easily penetrate in a skewered manner. Particularly preferred are cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin because they are easily included in the axis molecules in a solvent.

The number of cyclic molecules in one molecule of the polyrotaxane of the present invention (inclusion amount: the number of cyclic molecules penetrated by the axial molecule) is not particularly limited and can be appropriately selected depending on the purpose, but on average 5. ~200 is preferred. Further, assuming that the maximum inclusion amount of cyclic molecules is 1, the number of cyclic molecules in one molecule of the polyrotaxane of the present invention is preferably 0.01 to 0.95, more preferably 0.02 to 0.8, and more preferably 0.01 to 0.95. 05 to 0.6 is particularly preferred. Here, the maximum amount of inclusion of the cyclic molecule can be determined by the length of the axial molecule and the thickness of the cyclic molecule. Note that when the axis molecule is polyethylene glycol and the cyclic molecule is an α-cyclodextrin molecule, the maximum inclusion amount has been determined experimentally (see Macromolecules 1993, 26, 5698-5703). If the amount of inclusion of cyclic molecules is small, a relatively rigid structure will not be formed and the effect of improving mechanical strength will be insufficient, or the polyrotaxane molecules of the present invention will not be included with each other or with other polyrotaxane molecules of the present invention. It becomes difficult to obtain the effect of improving mechanical strength and the effect of improving adhesiveness due to interaction formation with the substance. In addition, when the amount of inclusion of the cyclic molecule is large, the molecular structure of the polyrotaxane of the present invention becomes too rigid, and the cyclic molecule is included in the axial molecule and can move around the axial molecule. "Pulley effect" is less likely to occur, and interactions between the polyrotaxane molecules of the present invention or between the polyrotaxane molecules of the present invention and other substances are less likely to be formed due to steric hindrance, resulting in improved mechanical strength and adhesive properties. The effect may be insufficient.

In the polyrotaxane of the present invention, the shaft molecule is preferably a molecule having a chain portion within the molecule that can include two or more cyclic molecules. The axial molecule in the polyrotaxane of the present invention has a chain part within the molecule that can include two or more cyclic molecules, and the cyclic molecule is included in the chain part. As long as both ends of the chain part (the part that allows the cyclic molecule to move in the axial direction around the chain part) are blocked with blocking groups to prevent the cyclic molecule from detaching from the chain part, the axis A portion of the molecule other than the chain portion may have one or more branch points as appropriate. That is, the axial molecule in the polyrotaxane of the present invention may be an axial molecule that does not have a branch point in the main chain, and if it has a chain part that can include two or more cyclic molecules, it can be used as a graft polymer or dendrimer. It may also be a branched molecule having one or more branch points, such as a star polymer or a star polymer.

The structure of known polyrotaxanes can be appropriately selected as the axis molecule in the polyrotaxane of the present invention. For example, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyisoprene, polyisobutylene, polyisobutene, polybutadiene, polytetrahydrofuran, Acrylic esters, polydimethylsiloxane, polyethylene, polymethyl vinyl ether, polypropylene, polyperfluorooxypropylene, oligotetrafluoroethylene, polycaprolactam, etc. are preferred because their structures are simple and the polyrotaxane of the present invention can be easily prepared. . Two or more types of these axial molecules may be mixed in the polyrotaxane of the present invention.

After creating a pseudopolyrotaxane (one in which a capping group is not introduced at both ends of the chain part but the shaft molecule passes through the cyclic molecule) or polyrotaxane using these shaft molecules, the pseudopolyrotaxane or polyrotaxane molecule is A crosslinked polyrotaxane obtained by crosslinking them can also be used as the polyrotaxane of the present invention. Such a crosslinked structure may be formed by crosslinking two or more cyclic molecules of pseudopolyrotaxane or rotaxane with each other, or by crosslinking two or more cyclic molecules of pseudopolyrotaxane or rotaxane with an axial molecule. Alternatively, it may be formed by crosslinking the axial molecules of two or more pseudopolyrotaxanes or rotaxanes. Further, it has at least one open end portion and a chain portion connected thereto, the open end portion can skewer a cyclic molecule, and the cyclic molecule is included in the chain portion in a skewer shape. A cross-linked molecule having a possible structure can also be used as an axis molecule in the polyrotaxane of the present invention, and a cross-linked molecule having one or more such chain parts is used to prepare a pseudopolyrotaxane, A crosslinked polyrotaxane may then be prepared by capping the open end portion with a capping group. In addition, a pseudopolyrotaxane is prepared by linking multiple cyclic molecules in advance through covalent bonds, ionic bonds, etc., and including them in a skewered manner with a shaft molecule, and then blocking the open end portion of the shaft molecule with a blocking group. A crosslinked polyrotaxane may be prepared by doing so. In addition, in the obtained crosslinked polyrotaxane, a structure in which the axial molecule penetrating the cyclic molecule is crosslinked can also be regarded as the axial molecule in the polyrotaxane of the present invention. Further, it has at least one open end portion and a chain portion connected thereto, the open end portion can skewer a cyclic molecule, and the cyclic molecule is included in the chain portion in a skewer shape. Cross-linked molecules with possible structures can also be used as axis molecules in the polyrotaxanes of the invention. In the crosslinked polyrotaxane, the crosslinking bond may be a chemical bond with a hydroxyl group, an amino group, a carboxyl group, an epoxy group, a vinyl group, a thiol group, or a photocrosslinking group of a cyclic molecule or an axial molecule, or any combination thereof. It may also be a chemical bond using an agent.

The weight average molecular weight of the shaft molecule in the polyrotaxane of the present invention is preferably from 500 to 1,000,000, particularly preferably from 1,000 to 100,000, and even more preferably from 2,000 to 50,000. When the weight average molecular weight of the axial molecule in the polyrotaxane of the present invention is less than 500, the rates of the inclusion reaction and unclathration reaction by the axial molecule of the cyclic molecule are competitive, making it difficult to introduce the blocking group in the clathrated state. difficult and difficult to synthesize. Furthermore, if the weight average molecular weight of the axial molecule in the polyrotaxane of the present invention exceeds 1,000,000, the solubility of the polyrotaxane in a solvent may be poor, and the synthesis may also be difficult. In addition, if the weight average molecular weight of the axial molecule in the polyrotaxane of the present invention is too small, it may be difficult to obtain the effect of improving mechanical strength or adhesiveness. If it is too high, the compatibility, solubility, and compatibility of the polyrotaxane of the present invention with the polymerizable monomer included in the adhesive composition of the present invention described below may deteriorate, making it difficult to obtain high adhesiveness. Note that the weight average molecular weight is determined using gel permeation chromatography (hereinafter sometimes abbreviated as "GPC"). If the shaft molecule is soluble in water or alcohol, calculate the weight average molecular weight in terms of polyethylene glycol. If the shaft molecule is insoluble in water, calculate the weight average molecular weight in terms of polystyrene using a solvent such as THF. , all you have to do is ask.

The blocking group in the polyrotaxane of the present invention is a group that is placed at both ends of the chain portion of the axial molecule and can maintain an inclusion state in which the cyclic molecule is pierced by the axial molecule in a skewered manner. This is a group that does not allow the cyclic molecule to fall off from the end. The blocking group in the polyrotaxane of the present invention includes a coumarin derivative. Coumarin derivatives include 7-diethylaminocoumarin, 7-carboxymethoxycoumarin, 7,8-biscarboxymethoxycoumarin, and 7-dicarboxymethylminocumarin (Chemical Society Reviews 2015, 44, 3358-3377). 7-diethylaminocoumarin is suitable because its absorption wavelength can be extended to about 360 nm, and it can be decomposed with high efficiency, such as about 100%, by ultraviolet rays of such a long wavelength. The coumarin derivative may be bonded to the end of the chain portion of the shaft molecule in the polyrotaxane of the present invention via a linker such as an ester bond, amide bond, carbonate bond, or carbamate bond. As an example, the chemical formula of a compound in which a linker is attached to 7-diethylaminocoumarin is shown below. R in the chemical formula represents a linker that connects the end of the chain portion of the axial molecule and the coumarin derivative. The coumarin derivative is not particularly limited and can be appropriately selected depending on the purpose, but 7-diethylaminocoumarin derivatives having the structure of the following chemical formula are preferred.

In the polyrotaxane of the present invention, the capping groups only need to contain coumarin derivatives, and not all of the capping groups need to be coumarin derivatives, but preferably, substantially all of the capping groups are coumarin derivatives. The coumarin derivative contained as a blocking group in the polyrotaxane of the present invention is a degradable group, and when exposed to ultraviolet light, which is a decomposition-inducing factor, the decomposable group decomposes and the structure of the polyrotaxane of the present invention collapses. Furthermore, if the cured product obtained by polymerizing the adhesive composition containing the polyrotaxane of the present invention and the polymerizable monomer described below is exposed to ultraviolet rays, the coumarin derivative, which is a decomposable group, will be decomposed. As a result, the adhesive layer, which is the cured product, may be easily detached because it decomposes, resulting in a decrease in the mechanical strength of the adhesive layer that is the cured product, and a decrease in the adhesion of the adhesive layer at the adhesive interface. can. That is, by using the polyrotaxane of the present invention containing a coumarin derivative as a blocking group, it is possible to provide an adhesive composition from which the cured adhesive layer can be freely removed when desired.

The polyrotaxane of the present invention may contain various functional groups or polymer chains in either or both of the cyclic molecule and the axial molecule in order to improve familiarity and compatibility with the polymerizable monomer.

Such functional groups include, but are not particularly limited to, acetyl groups, alkyl groups, trityl groups, tosyl groups, trimethylsilane groups, phenyl groups, and the like. On the other hand, such polymer chains include, but are not particularly limited to, oxyethylene chains, alkyl chains, acrylic ester chains, and the like. Further, the polymer chain may have a hydroxyl group, an amino group, an epoxy group, a vinyl group, a photocrosslinking group, or any combination thereof in the main chain or side chain. These polymer chains may be homopolymers or copolymers, and in the case of copolymers, they may be composed of two or more types of monomers, and may be block copolymers, alternating copolymers, random copolymers, or graft copolymers. When the cyclic molecule in the polyrotaxane of the present invention is cyclodextrin, various functional groups or polymer chains may be introduced into the hydroxyl groups of the cyclodextrin.

The polyrotaxane of the present invention may contain a polymerizable group in at least one of the cyclic molecule and the axial molecule. When the polymerizable monomer contained in the adhesive composition of the present invention is polymerized in the presence of the polyrotaxane of the present invention containing such a polymerizable group, the polyrotaxane of the present invention is Copolymerizes with monomers. In that case, polymerization also occurs between the polyrotaxanes of the present invention containing the aforementioned polymerizable groups. In particular, when a plurality of polymerizable groups are introduced into the polyrotaxane of the present invention, the polyrotaxane of the present invention becomes a crosslinking point in the cured product of the adhesive composition of the present invention, and the adhesive composition of the present invention becomes a crosslinking point. In some cases, the mechanical strength of the cured product of the adhesive composition of the present invention can be further increased, or part or all of the mechanical strength of the cured product of the adhesive composition of the present invention can be borne by the crosslinked structure of the polyrotaxane. Alternatively, for example, the adhesive composition of the present invention may contain a polymerizable monomer (for example, an acidic group-containing methacrylate, a sulfur atom-containing methacrylate, or a coupling group-containing methacrylate) that has adhesive properties to an object to be adhered. acrylate, etc.) and, if necessary, other polymerizable monomers, the polymerizable monomers contained in the adhesive composition of the present invention are polymerized in the presence of the polyrotaxane of the present invention. After curing the adhesive composition of the present invention and adhering an object at the adhesive interface, a polymerizable material having adhesive properties to the object and to the object near the adhesive interface is formed. Since the monomers, the polyrotaxane of the present invention, and other polymerizable monomers included as necessary are integrated by chemical bonding, the polyrotaxane of the present invention also has an adhesive property of the adhesive composition of the present invention. Contributes to sexual expression. In particular, when the polyrotaxane of the present invention is directly involved in part or all of the effect of improving the mechanical strength or the effect of developing adhesive properties of the adhesive composition of the present invention, the blocking group in the polyrotaxane of the present invention may be After the decomposition of a certain coumarin derivative, the structure of the polyrotaxane of the present invention collapses, and the above-mentioned mechanical strength improvement effect or adhesion development effect is greatly and directly lost, so a large adhesion reduction effect cannot be obtained. , is suitable.

The polymerizable group that the polyrotaxane of the present invention may contain in at least one of the cyclic molecule and the axial molecule includes conventionally known polymerizable groups. In particular, when the adhesive composition of the present invention is for biological hard tissues, the polymerizable groups that can be preferably used are (meth)acryloyl group and derivative groups of (meth)acryloyl group such as (meth)acryloyloxy group, (meth)acryloylamino group, and (meth)acryloylthio group; vinyl group; aryl group; styryl group, and (meth)acrylamide group, because they are less harmful to the body. The polyrotaxane of the present invention may contain multiple types of polymerizable groups.

The number average molecular weight of the polyrotaxane of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably about 5,000 to 60,000. When the polyrotaxane of the present invention contains a polymerizable group, the number average molecular weight of the polyrotaxane of the present invention containing a polymerizable group is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably about 5,000 to 120,000. preferable.

Preferred cyclic molecules in the polyrotaxane of the present invention are cyclodextrins, with α-cyclodextrin being particularly preferred.

The method for producing polyrotaxane of the present invention will be explained below. The polyrotaxane of the present invention can be produced according to a known method. For example, it can be manufactured according to a known manufacturing method (Japanese Patent Laid-Open Nos. 2011-46917 and 2012-25923). More specifically, the method for producing polyrotaxane of the present invention can be carried out, for example, as follows. First, synthesize and obtain an axial molecule and a cyclic molecule. The axial molecule and the cyclic molecule are then generally mixed in solution in a solvent in which they are commonly dissolved. As a result, the cyclic molecule is included in the axial molecule in the solution due to intermolecular forces, hydrophilic and hydrophobic interactions, and pseudopolyrotaxane is produced. By appropriately setting the reaction time and concentration at this time, the number of cyclic molecules (inclusion amount) in one molecule of pseudopolyrotaxane can be changed. For example, when polyethylene glycol and α-cyclodextrin with a molecular weight of several thousand to tens of thousands are dissolved in distilled water and stirred for several minutes to several hours, a pseudopolyrotaxane in which polyethylene glycol and α-cyclodextrin are included is precipitated. When the pseudopolyrotaxane becomes insolubilized in the solvent, the pseudopolyrotaxane is washed and recovered by filtration or centrifugation. Furthermore, if the pseudopolyrotaxane is soluble in the solvent, it is washed and recovered by dialysis or ultrafiltration. After redissolving the obtained pseudopolyrotaxane in a solvent as necessary, a coumarin derivative, which is a blocking group, is introduced into the open end of the chain portion of the axial molecule of the pseudopolyrotaxane, and unreacted reagents are added as necessary. etc. are purified and removed by dialysis or ultrafiltration to obtain the polyrotaxane of the present invention. When the polyrotaxane of the present invention contains a functional group, a polymer chain, or a polymerizable group, a functional group, a polymer chain, or a polymerizable group may be further introduced into the obtained polyrotaxane of the present invention as necessary. , crosslinking reaction, etc., to obtain the polyrotaxane of the present invention containing a functional group, a polymer chain, or a polymerizable group.

The present invention provides an adhesive composition containing the polyrotaxane of the present invention described above and a polymerizable monomer. Hereinafter, the adhesive composition of the present invention will be explained first, starting with the polymerizable monomer.

The polymerizable monomer contained in the adhesive composition of the present invention can be formed into a polymer (usually a polymer) through a polymerization reaction such as addition polymerization, polyaddition reaction, polycondensation reaction, or addition condensation in the presence of the polyrotaxane of the present invention. A cured product of the adhesive composition of the invention can be obtained by forming a polymer containing other components in the adhesive composition of the invention and curing the adhesive composition of the invention. The cured product of the adhesive composition of the present invention forms, for example, an adhesive layer. Examples of the polymerization reaction include conventionally known polymerization reactions such as chain polymerization, sequential polymerization, and living polymerization (see Polymer Synthesis, Junji Furukawa, Kagaku Dojin, 1986). The polymerizable monomer contained in the adhesive composition of the present invention has at least one conventionally known polymerizable group such as a polymerizable unsaturated group, a ring-opening polymerizable group, or a polycondensable group in the molecule. Any conventionally known polymerizable monomer that has been used in a conventionally known adhesive composition may be used as the polymerizable monomer contained in the adhesive composition of the present invention without limitation. Can be done. The polymerizable monomer contained in the adhesive composition of the present invention initiates polymerization by, for example, the action of heat, a polymerization initiator, gamma rays, electrolysis, plasma, or the like.

Examples of addition polymerization occurring in the polymerizable monomer contained in the adhesive composition of the present invention include radical polymerization, anionic polymerization, cationic polymerization, ring-opening polymerization, and the like.

The polymerizable monomer that undergoes addition polymerization to be included in the adhesive composition of the present invention is a conventionally known vinyl monomer (having a structure of CH ₂ ═CHX or CH ₂ ═C(-R)X, where X is NO ₂ , CN, COOR', -C(=O)R', -SO ₃ R', F, Cl, Br, OCH ₃ , OC(=O)R', NR'R'', etc., and here R, R', R'' are arbitrary substituents) or vinylidene monomer (having the structure CH ₂ = C (-X) Y, X and Y may be the same or different, NO ₂ , CN, COOR', -C(=O)R', -SO ₃ R', F, Cl, Br, OCH ₃ , OC(=O)R', NR'R'', etc., where (R, R', R'' are arbitrary substituents), cyclic ether, vinyl ether, etc. Specific examples include isobutyl vinyl ether, methyl vinyl sulfide, N-vinyl carbazole, isoprene, propylene, vinyl acetate, ethylene, nitroethylene, methylene methyl malonate, ethyl α-cyanoacrylate, ethyl α-cyanosorbate, and vinyl chloride. , vinylidene chloride, methyl methacrylate, phenyl methacrylate, methyl acrylate, methyl vinyl ketone, acrylonitrile, acrylamide, maleic anhydride, vinylidene cyanide, styrene, diolefin, alkylene oxide, lactam, vinyl ether, cyclic ether, 2,3 -Dichlorobutadiene, isobutyl vinyl ether, m-divinylbenzene, ethyl vinyl sulfide, phenyl vinyl sulfide, N-vinylcarbazole, lactone, α-methylstyrene, isoprene, ethyl vinyl ether, N-vinylpyrrolidone, 1-vinylnaphthalene, t-butyl Vinyl sulfide, butadiene, p-methylstyrene, isobutene, vinyl fluoride, vinyl fumarate, p-vinylphenol, 5-ethyl-vinylpyridine, oxazoline, aldehyde, ethylene oxide, epichlorohydrin, tetrahydrofuran, trioxane, norbornene, siloxane , phosphazene and the like.

Polymerization reactions occurring in the polymerizable monomers included in the adhesive composition of the present invention include polyaddition reactions. Polyaddition reactions occurring in the polymerizable monomers included in the adhesive composition of the present invention include alcohols (R-OH, R is an arbitrary substituent), amines (H-N(-R)(R''), R and R'' are arbitrary substituents), mercaptan (H-SR, R is an arbitrary substituent), and other active hydrogen compounds are added to double bonds or triple bonds, epoxy, aziridine , reaction of ring-opening addition of alcohol, amine, mercaptan to the ring-opening polymerizable functional group of ring-opening polymerizable monomers such as lactones and lactams, cycloaddition (using cycloaddition using a diene to a conjugated double bond) Examples of the polymerizable monomer that causes a polyaddition reaction to be included in the adhesive composition of the present invention include tolylene diisocyanate and tolydine diisocyanate, which are used in the synthesis of polyurethanes. Isocyanate polymers such as diisocyanates, adduct polyisocyanates, isocyanate dimers, and isocyanate trimer groups; polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and sucrose; Examples of the polymerizable monomers that cause a polyaddition reaction to be included in the adhesive composition of the present invention include diisocyanates and diazabidicrons used in the synthesis of polyurea. Also mentioned are diamines such as decene and triethylenediamine. Polymerizable monomers that undergo a polyaddition reaction and are included in the adhesive composition of the present invention include bisketene, biscarbodiimide, bismaleimide, dithiol, mercaptans (HS ( _CH2 )nSH), bisacrylamide, bisacryl ester, epichlorohydrin, bisphenol A, and the like.

The polymerization reaction that occurs in the polymerizable monomer included in the adhesive composition of the present invention includes a polycondensation reaction. Examples of polymerizable monomers that undergo polycondensation reactions included in the adhesive composition of the present invention include dicarboxylic acids such as dimethyl terephthalate used in the synthesis of polyesters, diols such as ethylene glycol, and diols used in the synthesis of polycarbonates. Examples include bisphenol A and phosgene, synthetic raw materials for polysulfone and polybenzyl, phenol, urea, melamine, xylene, and formaldehyde, which are synthetic raw materials for phenol resins, amino resins, and xylene resins.

Further, examples of the polymerizable monomer included in the adhesive composition of the present invention include various coupling agents and various silane compounds that are raw materials for synthesizing inorganic polymers.

The polymerizable monomers included in the adhesive composition of the present invention can be used alone or in combination of two or more.

When the adhesive composition of the present invention is used for biological hard tissues such as bones, nails, and dentistry, the biotoxicity of the polymerizable monomer itself included in the adhesive composition of the present invention, and the polymerization Considering the biotoxicity of the polymerization initiator used in conjunction with the polymerization reaction of the monomer as necessary, and also considering that it can be polymerized and cured under relatively mild conditions, the present invention As the polymerizable monomer to be included in the adhesive composition, it is preferable to use a monomer having an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, a styryl group, etc. as a polymerizable group.

When the adhesive composition of the present invention is used for biological hard tissue (particularly when the adhesive composition of the present invention is used for dentistry considering use in the oral cavity), the adhesive composition of the present invention is used for dental purposes. Examples of suitable polymerizable monomers to be included in the adhesive composition of the invention include 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, and allyl (meth)acrylate. , tetrahydrofurfuryl (meth)acrylate, 2-(meth)acryloxyethyl propionate, 2-methacryloxyethyl acetoacetate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, glyceryl mono( Monofunctional ones such as meth)acrylate, polyethylene glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate , nonaethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate Aliphatic products having two or more polymerizable unsaturated groups such as acrylate, pentaerythritol tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, urethane(meth)acrylate; 2,2-bis((meth)acryloxyphenyl)propane, 2,2-bis[4-(2-hydroxy-3-(meth)acryloxyphenyl)]propane, 2,2-bis(4-(meth)acryloxyphenyl)propane ) acryloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, and other polymerizable unsaturated Aromatic compounds having two or more groups; alkyl and cycloalkyl α-cyano such as methyl α-cyanoacrylate, ethyl α-cyanoacrylate, propyl α-cyanoacrylate, butyl α-cyanoacrylate, and cyclohexyl α-cyanoacrylate Acrylates; alkenyl and cycloalkenyl α-cyanoacrylates such as allyl α-cyanoacrylate, methallyl α-cyanoacrylate, and cyclohexenyl α-cyanoacrylate; alkynyl α-cyanoacrylates such as propangyl α-cyanoacrylate Aryl α-cyanoacrylates such as phenyl α-cyanoacrylate and toluyl α-cyanoacrylate; Alkoxy α-cyanoacrylates such as methoxyethyl α-cyanoacrylate and ethoxyethyl α-cyanoacrylate; furfuryl α-cyanoacrylate, etc. α-cyanoacrylate having a heterocyclic group; α-cyanoacrylate having a silyl group such as trimethylsilylmethyl α-cyanoacrylate, trimethylsilylethyl α-cyanoacrylate, trimethylsilylpropyl α-cyanoacrylate, dimethylvinylsilylmethyl α-cyanoacrylate 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitic acid and its anhydride, 2-methacryyloxyethyl dihydrogen phosphate, bis(2 - Acidic group-containing (meth)acrylates such as methacryloyloxyethyl) hydrogen phosphate and 10-methacryloyloxydecyl dihydrogen phosphate; Basic group-containing (meth)acrylate monomers such as N,N-dimethylaminoethyl methacrylate ; sulfur atom-containing (meth)acrylates such as ω-methacryloyloxyhexyl 2-thiouracil-5-carboxylate; coupling group-containing (meth)acrylates such as γ-methacryloxypropyltrimethoxysilane; diacetone acrylamide, N- Containing (meth)acrylamide groups such as methylol(meth)acrylamide; styrene, α-methylstyrene derivatives; trimethylene oxide, 3-methyl-3-oxetanylmethanol, 1,4-bis(3-ethyl) Those with an oxetane ring such as -3-oxetanylmethyloxy)benzene, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether; diglycerol polydiglycidyl ether, pentaerythritol polyglycidyl ether, ethylene glycol-bis(3, Epoxy compounds such as 4-epoxycyclohexanecarboxylate); aziridine compounds, azetidine compounds, episulfide compounds, cyclic acetals, bicycloorthoesters, spiroorthoesters, cyclic carbonates, spiroorthocarbonates, tetrahydrofuran, and the like.

The polymerizable monomer included in the adhesive composition of the present invention preferably has two or more polymerizable groups for the purpose of further increasing polymerizability for use in biological hard tissues. The polymerizable monomer included in the adhesive composition of the present invention for biological hard tissue is particularly preferably a (meth)acrylate-based polymerizable monomer because it has high polymerizability and low toxicity to living organisms. In addition, suitable polymerizable monomers to be included in the adhesive composition of the present invention for use in living body hard tissues, especially dentistry, include living body hard tissues, especially teeth (enamel). methacrylates containing acidic groups, as they have high adhesion to ceramics and metals (especially non-noble metals) that are present in close proximity or adhesion during the treatment of biological hard tissues. Sulfur atom-containing methacrylates are mentioned because they have high adhesion to noble metals that are present in close proximity or adhesion when treating biological hard tissues, and ceramics and A coupling group-containing methacrylate is mentioned because it has high adhesiveness to organic-inorganic composite materials.

Polymerization of the polymerizable monomer contained in the adhesive composition of the present invention can be initiated by the action of heat, a polymerization initiator, gamma rays, electrolysis, plasma, etc., for example.

The method for initiating such polymerization is not particularly limited, and conventionally known polymerization initiation methods can be employed. For example, in thermal polymerization, gamma ray polymerization, electrolytic polymerization, and plasma polymerization, until a practically sufficient degree of polymerization is obtained, preferably, until the initial shear adhesion test force reaches a required value of 0.5 MPa or more, Heating, gamma ray irradiation, energization, and plasma irradiation are performed under the conditions set (temperature, irradiation intensity, amount of current, voltage, and time).

In order to initiate such polymerization, a polymerization initiator can be used, and conventionally known radical polymerization, anionic polymerization, cationic polymerization, polyaddition reaction, polycondensation reaction, coupling reaction, inorganic synthetic polymer synthesis, etc. Conventionally known polymerization initiators used in can be used (see Polymer Synthesis, Junji Furukawa, Kagaku Dojin, 1986). Examples of radical polymerization initiators include peroxides such as cumene peroxide, tert-butyl peroxide, dicumyl peroxide, and benzoyl peroxide, azo compounds such as azoisobutyronitrile, and Fenton's reagent ( Redox initiators such as hydrogen peroxide/Fe ²⁺ ), benzoyl peroxide/dimethylaniline, hydroperoxide/mercaptan, alkyl borons, alkyl halides/metals (Fe, Co, Ni, Cu), Mn acetylacetonate, iodonium salts photopolymerization initiators such as and sulfonium salts. Examples of anionic polymerization initiators include metals such as K, Na, and Li, alkyl metals such as SrR ₂ , CaR ₂ , KR, NaR, and LiR, alcoholates such as ROK, RONa, and ROLi, strong alkalis, and amines such as pyridine. Examples include water, water, etc. For cationic polymerization, Lewis acids such as BF ₃ , SnCl ₄ , EtAlCl ₂ , ZnCl ₂ , Et ₂ Zn, etc., and cationic polymerization initiators disclosed in JP-A No. 2005-187545 can be used. Initiators used in the Ziegler method and Ziegler-Natta method (TiCl ₄ and Et ₃ Al, etc.) can also be used.

When the adhesive composition of the present invention is used for biological hard tissue, it is used as an anionic polymerization initiator or a radical polymerization initiator used in the following photopolymerization because it is less harmful to living organisms or the polymerization reaction conditions are mild. Agents are preferably used. That is, as the radical polymerization initiator used for photopolymerization, which is preferably used in the adhesive composition of the present invention for biological hard tissue, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Alkyl ethers, benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, benzophenones such as benzophenone, 4,4'-dimethylbenzophenone and 4-methacryloxybenzophenone, diacetyl, 2,3-pentadionebenzyl, camphorquinone, α-diketones such as 9,10-phenanthraquinone and 9,10-anthraquinone, thioxanthone compounds such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone, and methylthioxanthone, bis-(2 ,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis- Acylphosphine oxides such as (2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Can be mentioned.

Reducing agents are often added to radical polymerization initiators used in photopolymerization. Examples of reducing agents include tertiary amines such as 2-(dimethylamino)ethyl methacrylate, ethyl 4-dimethylaminobenzoate, and N-methyldiethanolamine, aldehydes such as lauryl aldehyde, dimethylaminobenzaldehyde, and terephthalaldehyde, and sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and thiobenzoic acid.

Further, examples of the polymerization initiator that can be used for polymerizing the polymerizable monomer contained in the adhesive composition of the present invention include thermal polymerization initiators, and examples of the thermal polymerization initiator include: Peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, azobisisobutyronitrile, etc. boron compounds such as tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis(p-fluororophenyl)borate, triethanolamine salt of tetraphenylborate, 5-butylbarbituric acid , barbituric acids such as 1-benzyl-5-phenylbarbituric acid, and sulfinate salts such as sodium benzenesulfinate and sodium p-toluenesulfinate.

Examples of the polymerization initiator that can be used for polymerizing the polymerizable monomer contained in the adhesive composition of the present invention include chemical polymerization initiators, and examples of the chemical polymerization initiator include radical polymerization initiators. Organic peroxides/amines, organic peroxides/amines/organic sulfinic acids, organic peroxides/amines/arylborates, arylborates/acidic compounds, arylborates/acidic compounds/organic peroxides, Examples include various combinations of oxides, arylborates/acidic compounds/transition metal compounds, and barbituric acid derivatives/copper compounds/halogen compounds.As anionic polymerization initiators, amines such as pyridine, water, etc. Can be mentioned.

These polymerization initiators may be used alone or in combination of two or more. A dual cure type can also be obtained by combining a photopolymerization initiator and a chemical polymerization initiator.

(Other optional ingredients)
The adhesive composition of the present invention may further contain other optional ingredients as necessary. For example, the adhesive composition of the present invention includes pigments for adjusting the color tone of the adhesive composition, colorants such as fluorescent pigments and dyes, stabilizers such as pH adjusters such as amines, quartz, precipitated silica, Strength modifiers such as inorganic particles such as precipitated zirconia, precipitated titania, composite oxides such as silica-zirconia, or organic particles such as polyalkyl methacrylate, polymers dissolved in the adhesive composition of the present invention, fumed silica, etc. Viscosity modifiers, various salts, organic solvents such as ethanol, isopropanol, ethylene glycol, propanediol, acetone, solvents such as water, various fragrances, various antibacterial agents, various medicinal ingredients, 2-(2-benzotriazole)-p- It may also contain ultraviolet absorbers such as cresol, various polymerization inhibitors such as butylated hydroxytoluene and methoxyhydroquinone, various antioxidants, and the like. The adhesive composition of the present invention preferably contains a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, or 2,6-ditertiary butylphenol, in order to particularly improve storage stability and environmental light stability.

The blending amount of the polyrotaxane of the present invention and the blending amount of the polymerizable monomer to be blended in the adhesive composition of the present invention are not particularly limited, but 100 mass of the polymerizable monomer to be blended in the adhesive composition of the present invention The amount of the polyrotaxane of the present invention blended into the adhesive composition of the present invention is preferably 0.1 parts by mass to 1000 parts by mass, and within the range of 1 part by mass to 800 parts by mass. More preferably, the amount is within the range of 5 parts by weight to 500 parts by weight. In the adhesive composition of the present invention, if the amount of the polyrotaxane of the present invention blended is too small, the effect of reducing adhesiveness due to decomposition of the coumarin derivative, which is a blocking group, becomes difficult to manifest. In the adhesive composition of the present invention, when the amount of the polyrotaxane of the present invention exceeds 1000 parts by mass based on 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the adhesive composition of the present invention has the adhesive property of the present invention. There is a possibility that compatibility with the polymerizable monomer contained in the composition will be extremely reduced, making it difficult to use as an adhesive.

When a polymerization initiator is blended into the adhesive composition of the present invention to polymerize the polymerizable monomer contained in the adhesive composition of the present invention, there are no particular limitations on the blend amount as long as it is an effective amount, but the blend amount of the polymerization initiator blended into the adhesive composition of the present invention is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymerizable monomer blended into the adhesive composition of the present invention.

The method for producing the adhesive composition of the present invention is not particularly limited, and any known method for producing an adhesive composition may be used. That is, the adhesive composition of the present invention includes, for example, the above-mentioned polymerizable monomer and the polyrotaxane of the present invention to be included in the adhesive composition of the present invention, if necessary. It can be manufactured by mixing with other components. When the adhesive composition of the present invention contains a polymerization initiator, and the polymerization initiator is a photopolymerization initiator, generally, a predetermined amount of each component to be blended is weighed out under light shielding, and the ingredients are uniformly mixed. The adhesive composition of the present invention can be manufactured by kneading up to

The adhesive composition of the present invention can be obtained by polymerizing the polymerizable monomer contained in the adhesive composition of the present invention in the presence of the polyrotaxane of the present invention to cure the adhesive composition of the present invention. A cured product of the adhesive composition of the present invention having higher mechanical strength than the adhesive composition of the present invention before curing can be obtained, and high adhesiveness can be obtained. The cured product can be, for example, an adhesive layer. Therefore, the adhesive composition of the present invention can be used to adhere an object to an object or to form an adhesive layer on an object.

Even when the adhesive composition of the present invention is cured to obtain a cured product of the adhesive composition of the present invention, the polyrotaxane of the present invention preferably exists in the cured product of the adhesive composition of the present invention with the coumarin derivative contained as a blocking group being substantially undecomposed, i.e., usually 70% or more, preferably 80% or more, being undecomposed. The polyrotaxane of the present invention itself present in the cured product of the adhesive composition of the present invention also contributes to maintaining and improving the strength of the cured product of the adhesive composition of the present invention as an ultra-high molecular compound. This is because (1) the polyrotaxane of the present invention is a relatively rigid molecule, which contributes to improving the mechanical strength, (2) the adhesion at the adhesive interface is improved due to the intermolecular interaction of the polyrotaxane of the present invention, the interaction between the polyrotaxane of the present invention and other components contained in the adhesive composition of the present invention, or the interaction between the polyrotaxane of the present invention and the adhesive interface of the object or target object to which the cured product of the adhesive composition of the present invention is adhered, or (3) the mechanical strength of the cured product of the adhesive composition of the present invention, such as the adhesive layer (cured layer) obtained after curing the adhesive composition of the present invention, is improved. Each of the above interactions occurs due to physical or chemical interactions or bonds such as compatibility, wettability, van der Waals forces, hydrogen bonds, ionic bonds, and covalent bonds.

After the adhesive composition of the present invention is applied to the surface of an object or object to be adhered, the polymerizable monomer contained in the adhesive composition of the present invention is polymerized in the presence of the polyrotaxane of the present invention. Then, the adhesive composition of the present invention is cured to obtain a cured product of the adhesive composition of the present invention, which is then used. In this use, after curing, for example, a solid adhesive layer (cured layer) is formed on the surface of the object or object, and the cured product of the adhesive composition of the present invention is attached to the object or object. It will be glued together. The adhesive composition of the present invention may be used by forming a cured product of the adhesive composition of the present invention, such as an adhesive layer (cured layer), on the surface of one object. Alternatively, the adhesive composition of the present invention is applied between at least one object and an object to cause polymerization for mutual adhesion of each of the at least one object and the object. The adhesive may be cured and used to bond the at least one object to the object. In this latter use, the adhesive composition of the invention will have adhesive properties to each of the at least one object and object.

Examples of objects or objects to which the adhesive composition of the present invention has adhesive properties include conventionally known processed products made of conventionally known materials and natural products. Examples of such materials include various metals, metal alloys, ceramics, wood, porcelain, glass, plastics, organic and inorganic composite materials, biological hard tissues such as teeth, nails, and bones, proteins such as skin, polysaccharides, and rock salt. Examples include inorganic salts such as, carbohydrates such as sugar, various natural inorganic substances such as shells, inorganic substances such as metal oxides such as jewelry, and rubbers such as silicone rubber and natural rubber.

The adhesive composition of the present invention can adhere to a target object through physical and chemical interactions such as adsorption, adhesion, adhesion (mainly through physical fusion), chemical adhesion (mainly through chemical bonding), or a combination thereof. It has adhesive properties to objects. The adhesive composition of the present invention preferably has the adhesive properties defined below. That is, the adhesive composition of the present invention is obtained by polymerizing the polymerizable monomer contained in the adhesive composition of the present invention in the presence of the polyrotaxane of the present invention to cure the adhesive composition of the present invention. Since the cured product of the adhesive composition of the present invention is used to form, for example, an adhesive layer (cured layer), considering its purpose and effects, the adhesive composition has a higher adhesiveness than that which can be easily removed. Adhesion (cohesiveness) is preferred. That is, suitable adhesive properties of the adhesive composition of the present invention include a flat plate made of the same material as the object or object to which the adhesive composition of the present invention is attached (depending on the shape and size of the object). (cut, polished, or resin-embedded), prepare a polished surface by polishing the surface of the object or object into a flat shape using P600 waterproof abrasive paper, and polish the polished surface as necessary. is treated with a pretreatment agent, a cylindrical mold with a diameter of 2 to 5 mm and a height of 2 to 5 mm is placed on top of the mold, and the adhesive composition of the present invention is filled into the mold so as not to contain air bubbles. Then, the adhesive composition of the present invention is cured by polymerization to obtain an adhesive test piece. Thereafter, a shear adhesion test is performed using a universal testing machine (Autograph, manufactured by Shimadzu Corporation). At that time, if an initial shear adhesion test force of 0.5 MPa or more, preferably 2 MPa or more, particularly preferably 5 MPa or more is obtained, the adhesive composition of the present invention exhibits suitable adhesion to the object or object. Defined as having. In addition, in the case of a composition that only has adhesive properties, it usually shows an initial shear adhesion test force of less than 0.5 MPa (for example, when a plastic rod with a diameter of 3 mm and a height of 3 mm is adhered with a commercially available double-sided tape). The shear adhesion test force is less than 0.5 MPa). Note that for objects or objects made of materials that cannot be polished with waterproof abrasive paper, another polishing means is used to polish them to a surface roughness equivalent to that of P600. Further, for objects or objects that are used with a surface roughness greater than P600 in actual use, an initial shear adhesion test may be conducted with the surface roughness in actual use. In addition, for objects and objects that are difficult to polish, such as those in the form of fibers such as non-woven fabrics, it is possible to conduct an initial shear adhesion test under actual conditions. good.

As shown in Examples below, the polyrotaxane of the present invention is decomposed by irradiation with ultraviolet light. Further, the adhesive composition of the present invention obtained by polymerizing the polymerizable monomer contained in the adhesive composition of the present invention in the presence of the polyrotaxane of the present invention and curing the adhesive composition of the present invention. The cured product is decomposed by irradiation with ultraviolet light, resulting in a decrease in mechanical strength and adhesiveness. Therefore, in adhesion using the cured product of the adhesive composition of the present invention, the adhesiveness can be reduced by irradiating the cured product with ultraviolet light.

That is, the present invention provides a method for reducing the mechanical strength of a cured body of the adhesive composition of the present invention, comprising a step of irradiating the cured body with ultraviolet light. For example, when removing an adhesive layer, which is a cured body of the adhesive composition of the present invention, from an object, or when removing an object adhered to an object by a cured body of the adhesive composition of the present invention from the object, the cured body can be decomposed by irradiating the cured body with ultraviolet light, thereby reducing the mechanical strength of the cured body and reducing the adhesiveness of the cured body. It is presumed that the cured body is decomposed by irradiation with ultraviolet light because the coumarin derivative, which is a blocking group that prevents the cyclic molecules contained in the polyrotaxane of the present invention from being detached, is decomposed by irradiation with ultraviolet light, and the cyclic molecules that were skewered and included by the axis molecule can be detached from the axis molecule, causing the structure of the polyrotaxane to collapse. When the polyrotaxane structure is destroyed by the decomposition of the coumarin derivative, which is a blocking group, as described above, a state is created in which relatively low molecular weight cyclic molecules (or linear molecules or low molecular weight compounds resulting from ring-opening of the cyclic molecules) exist independently (not in an inclusion state). In this case, the effect of improving the mechanical strength obtained because the polyrotaxane of the present invention described above is a relatively rigid molecule, the effect of improving the adhesion at the adhesion interface due to the intermolecular interaction of the polyrotaxane of the present invention, the interaction between the polyrotaxane of the present invention and other components contained in the adhesive composition of the present invention, or the interaction between the polyrotaxane of the present invention and an object or target to be adhered using the adhesive composition of the present invention, and the effect of improving the mechanical strength of the adhesive layer obtained after curing the adhesive composition of the present invention are lost, or in the case where the polyrotaxane of the present invention is insoluble in a solvent and the cyclic molecules (or linear molecules or low molecular weight compounds resulting from ring-opening of the cyclic molecules) show solubility in a solvent, the cyclic molecules in the adhesive layer dissolve and flow out of the adhesive layer, etc., resulting in a decrease in the adhesion at the adhesion interface and a decrease in the mechanical strength of the adhesive layer. As a result, the adhesiveness is reduced, and the adhesive layer obtained by polymerizing and curing the adhesive composition of the present invention can be easily removed from the target object, or the target object can be easily detached from the target object. The fact that the adhesive layer can be easily removed or detached can be examined, for example, as follows. That is, an adhesive test piece, which is the target cured body prepared in the same manner as in the measurement of the initial shear adhesion test strength described above, is irradiated with ultraviolet light for a predetermined time in a predetermined manner and under predetermined conditions. Then, a shear adhesion test is performed using a universal testing machine (autograph, manufactured by Shimadzu Corporation) to examine the shear adhesion test strength after irradiation with ultraviolet light. At that time, if the value obtained by dividing the shear adhesion test strength after irradiation with ultraviolet light by the initial shear adhesion test strength (shear adhesion test strength reduction effect) is 0.9 or less, preferably 0.8 or less, and more preferably 0.6 or less, it is determined that the target cured body can be easily removed or detached.

In the method for reducing the mechanical strength of the cured product provided by the present invention, the wavelength of the ultraviolet light irradiated to the cured product of the adhesive composition of the present invention is not particularly limited, but for example, from 320 to Irradiation with near-ultraviolet light of 400 nm is preferable because it can achieve both high safety for living organisms and sufficient reduction in adhesiveness of the cured product.

In the method for reducing the mechanical strength of the cured body provided by the present invention, the time for irradiating the cured body of the adhesive composition of the present invention with ultraviolet light is, for example, 2 to 30 minutes. If the time for irradiating with ultraviolet light is less than 2 minutes, there is a problem that the decomposition of the cured body is insufficient, and if the time for irradiating with ultraviolet light exceeds 30 minutes, there is a problem that the polyrotaxane is completely decomposed and no further change in the mechanical properties occurs.

The adhesive composition of the present invention can be used in various applications such as general industry, medical care, civil engineering, and daily life. The adhesive composition of the present invention has various properties, such as liquid, gel, wax, and solid that can be used after being dissolved, into a single composition. It can be used in combination or in an embodiment consisting of multiple compositions.

When the adhesive composition of the present invention is an embodiment consisting of one composition, the adhesive composition of the present invention is applied to a target object, and if necessary, the solvent contained in the adhesive composition of the present invention is dried. The adhesive composition of the present invention is obtained by curing the adhesive composition of the present invention by polymerizing the polymerizable monomer contained in the adhesive composition of the present invention in the presence of the polyrotaxane of the present invention. A cured product can be obtained to form, for example, an adhesive layer. Alternatively, the adhesive composition of the present invention is applied to a plurality of objects, the solvent contained in the adhesive composition of the present invention is dried and removed as necessary, and the plurality of objects are pressure-bonded. A polymerizable monomer contained in the adhesive composition is polymerized in the presence of the polyrotaxane of the present invention, and the adhesive composition of the present invention is cured to obtain a cured product of the adhesive composition of the present invention. By forming an adhesive layer, the plurality of objects can be bonded to each other.

Examples of embodiments in which the adhesive composition of the present invention is composed of a plurality of compositions include the following. For example, the adhesive composition of the present invention containing a polymerizable monomer and the polyrotaxane of the present invention comprises a pretreatment agent (primer) and an adhesive, and at least one of the pretreatment agent and the adhesive When the polymerizable monomer and the polyrotaxane of the present invention are packaged or coexist, first, the surface of the target object is treated with a pretreatment agent. Next, when the adhesive composition of the present invention contains a polymerizable monomer in the pretreatment material, the polymerizable monomer is polymerized as necessary, and then an adhesive is applied. Crimp other objects as necessary. When the adhesive composition of the present invention contains the polymerizable monomer in the adhesive, the polymerizable monomer is polymerized as necessary. Further, for example, the adhesive composition of the present invention containing a polymerizable monomer and the polyrotaxane of the present invention is composed of a plurality of adhesives, and at least one of the plurality of adhesives contains the polymerizable monomer. When the polyrotaxane of the present invention is packaged or coexisting, the plurality of adhesives are sequentially applied to the object (at this time, the plurality of adhesive layers applied sequentially may be cured separately and sequentially). , or by mixing a plurality of adhesives in advance and applying the adhesive to the target object, press-bonding other objects as necessary, and polymerizing the polymerizable monomer as necessary, to obtain the adhesive properties of the present invention. The composition is cured to form an adhesive layer. The adhesive composition of the present invention may be an adhesive composition comprising one or more pretreatment agents and one or more adhesives.

The cured product of the adhesive composition of the present invention obtained by polymerizing the polymerizable monomer contained in the adhesive composition of the present invention and curing the adhesive composition of the present invention can itself be used as a target material. The adhesive composition of the present invention can be used as an adhesive because it has adhesive properties to. That is, the present invention provides an adhesive comprising the adhesive composition of the present invention.

Examples of adhesives made of the adhesive composition of the present invention include adhesives between multiple objects, coating materials for objects, sealing materials, layer forming materials such as insulating layers and heat insulation layers, pretreatment agents, etc. Adhesive layer forming material (for example, another object or another adhesive layer is adhered or formed on this adhesive layer using the adhesive composition of the present invention or a conventionally known adhesive), Filling and repairing materials for recesses and hole-filling materials (for example, filling and repairing cracks, scratches, holes, etc. with the adhesive composition of the present invention), convex-forming materials and mounting materials (for example, filling and repairing cracks, scratches, holes, etc. with the adhesive composition of the present invention) An example of this method is to apply an adhesive composition onto the surface of an object, to cause polymerization and to cure the adhesive composition, thereby forming a structure made of a cured product of the adhesive composition of the present invention.

Examples of adhesives made of the adhesive composition of the present invention include α-cyanoacrylate as a polymerizable monomer contained in the adhesive composition of the present invention, and liquid or gel-like adhesives containing α-cyanoacrylate as a polymerizable monomer and the polyrotaxane of the present invention. The adhesive made of the adhesive composition of the present invention can be made by contacting and mixing with moisture in the atmosphere and a polymerization initiator such as a compound containing an OH group or an amino group. The polymerizable monomer contained in the adhesive composition of the present invention is polymerized in the presence of the polyrotaxane of the present invention, and the adhesive composition of the present invention is cured in a relatively short time (several seconds to several seconds). (after 1 minute) develops adhesion.

As shown in the examples below, the cured product of the adhesive composition of the present invention is decomposed by irradiation with relatively high wavelength and low toxicity ultraviolet light, so the adhesive composition of the present invention has high safety for living organisms. It can be used while being secured. Furthermore, as described above, although the adhesive composition of the present invention contains a polymerizable monomer and has high adhesive properties, the adhesive composition of the present invention may be decomposed by irradiation with ultraviolet rays, thereby reducing its adhesive properties. Therefore, it is possible to easily remove the adhesive layer from the target object or remove the target object adhered to the target object while reducing damage to the target object. Therefore, the adhesive composition of the present invention can be particularly used for biological hard tissues, and can be used for dental purposes such as adhesion of orthodontic brackets or temporary attachment of implants. That is, the adhesive composition of the present invention is suitable as an adhesive composition for biological hard tissues such as bones, nails, dentistry, and the like. In particular, the adhesive composition of the present invention can easily remove the adhesive layer from teeth weakened due to secondary caries or the like, and can easily remove objects to be adhered to, thereby reducing damage to tooth structure. Particularly preferred is a dental adhesive composition. Furthermore, especially during orthodontic treatment, cleaning becomes difficult and secondary caries tends to occur around orthodontic brackets, and the risk of damaging teeth when removing orthodontic brackets can be reduced. The adhesive composition can be particularly suitably used as an adhesive composition for adhering orthodontic brackets. When bonding orthodontic brackets, debonding (removal of the brackets) and rebonding (reattachment of the brackets) may be repeated depending on the progress of orthodontic treatment, and from that perspective, such use is particularly suitable. It becomes a mode. In addition, when the adhesive composition of the present invention is used as a temporary attachment for an implant superstructure, the superstructure can be destroyed when the superstructure needs to be removed for the purpose of cleaning around the implant. It can be removed without causing any damage or applying excessive force to the forehead bone. Therefore, the adhesive composition of the present invention can be particularly suitably used as an adhesive composition for temporarily attaching an implant such as an implant superstructure.

The adhesive composition of the present invention, which is used for biological hard tissues, will be mainly described below.

In the adhesive composition of the present invention, which is intended for living body hard tissues, examples of the living body hard tissues to be bonded include bones, nails, teeth (enamel and dentin), and the like. The main components of these compositions are inorganic components such as hydroxyapatite and proteins such as collagen. Therefore, the adhesive composition for biological hard tissue of the present invention may be one that can be commonly used for bones, nails, teeth, and the like.

The adhesive composition of the present invention can be applied to, for example, biological hard tissues and other articles to be adhered (metals (gold, silver palladium alloy, silver alloy, titanium alloy, etc.), plastics (made of polyalkyl methacrylate, polyester, polyamide, etc.). Restorations made of organic-inorganic composite materials, ceramics (porcelain, metal oxide ceramics such as alumina and zirconia), inorganic materials such as hydroxyapatite, and other biological hard tissues, Adhesives for articles such as jigs, correction tools, appliances, fillings, retainers, wires, screws, fixtures, etc., coating materials for biological hard tissues and other articles mentioned above, and seals for biological hard tissues and other articles mentioned above. material, a layer-forming material such as an insulating layer or a heat-insulating layer for biological hard tissue or other articles, and an adhesive layer-forming material such as a pre-treatment agent for biological hard tissue or other articles (e.g., on this adhesive layer, Furthermore, another object or another adhesive layer is adhered or formed using the adhesive composition of the present invention or a conventionally known adhesive.), a filling repair material for a recess in a biological hard tissue or the other article mentioned above. or hole-filling material (for example, the adhesive composition of the present invention fills and repairs cracks, scratches, holes, etc. in biological hard tissues or other articles mentioned above), forming convex portions in biological hard tissues or other articles mentioned above. material or mounting material (for example, the adhesive composition of the present invention is applied to the surface of a biological hard tissue or the other article mentioned above and cured by causing polymerization, and the adhesive composition of the present invention is made of a cured product of the adhesive composition of the present invention) It can be used as an adhesive to form structures.

When bonding biological hard tissues such as bones, nails, and teeth to articles made of materials such as metals, plastics, organic-inorganic composite materials, ceramics, and inorganic materials such as hydroxyapatite, the present invention is applicable to biological hard tissues. It is preferable that the adhesive composition has adhesive properties to these materials. For this purpose, if a sulfur atom-containing polymerizable monomer such as an SH group is used as a polymerizable monomer to be included in the adhesive composition of the present invention for biological hard tissues, adhesiveness to noble metals can be improved. If an acidic group-containing polymerizable monomer is used as the polymerizable monomer in the adhesive composition of the present invention for biological hard tissue, it will be possible to bond to non-noble metals, ceramics, and organic-inorganic composite materials. If a coupling group-containing polymerizable monomer such as methacryloxypropyltrimethoxysilane is used as the polymerizable monomer to be included in the adhesive composition of the present invention for biological hard tissue, Adhesiveness to organic-inorganic composite materials and ceramics can be obtained; if the adhesive composition of the present invention, which is used for biological hard tissue, contains an organic solvent to swell the surface, adhesiveness to plastics can be obtained. A method of introducing a merging group into the polyrotaxane of the present invention to improve adhesion is suitable.

In particular, considering that tooth regeneration is difficult with current technology and that teeth cannot be returned to their original state once they have been damaged, biohardening is important from the perspective of safe debonding. As mentioned above, the adhesive composition of the present invention that is used for tissues is preferably a dental adhesive composition, and in particular, as mentioned above, it is used for adhesion of orthodontic brackets or for implants. Particularly preferred is temporary wear.

--Coating material for biological hard tissue or sealing material for biological hard tissue (particularly, dental coating material or dental sealing material)--
The adhesive composition of the present invention, which is for use as a coating material for biological hard tissue or a sealing material for biological hard tissue (particularly a dental coating material or a dental sealing material), has adhesiveness to biological hard tissues such as bones, nails, teeth, etc., and can be polymerized and hardened to form an adhesive layer on the adhesion surface of the biological hard tissue. In general, the adhesive layer itself functions as a coating layer or a sealing layer, and therefore can be used, for example, for the purpose of protecting teeth on which the adhesive layer is formed from external stimuli (suppressing hypersensitivity) and for the purpose of improving the aesthetics of nails and making them less susceptible to scratches.

The amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention for biological hard tissues used as a coating material for biological hard tissues or a sealing material for biological hard tissues (particularly a dental coating material or a dental sealing material) is preferably within the range of 0.5 parts by mass to 500 parts by mass, more preferably within the range of 1 part by mass to 250 parts by mass, and most preferably within the range of 3 parts by mass to 200 parts by mass, relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. If the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention is less than 0.5 parts by mass relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the adhesive layer may not be sufficiently weakened after the structure of the polyrotaxane of the present invention is decomposed. Furthermore, if the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention exceeds 500 parts by mass per 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the viscosity may become too high, which may affect the operability of the coating material for biological hard tissue or the sealing material for biological hard tissue (particularly the dental coating material or dental sealing material).

In addition, the adhesive composition of the present invention for hard biological tissues used as a coating material for hard biological tissues or a sealing material for hard biological tissues (particularly a dental coating material or a dental sealing material) is suitable for containing a polymerization initiator because polymerization occurs and hardens quickly under relatively mild conditions. In this case, the amount of the polymerization initiator to be blended in the adhesive composition of the present invention is preferably within the range of 0.001 parts by mass to 20 parts by mass, more preferably within the range of 0.005 parts by mass to 15 parts by mass, and most preferably within the range of 0.01 parts by mass to 10 parts by mass, relative to 100 parts by mass of the polymerizable monomer to be blended in the adhesive composition of the present invention. By blending the amount of the polymerization initiator to be blended in the adhesive composition of the present invention in an amount of 0.001 parts by mass or more relative to 100 parts by mass of the polymerizable monomer to be blended in the adhesive composition of the present invention, it is possible to increase the polymerization hardening property during polymerization. In addition, the amount of polymerization initiator blended into the adhesive composition of the present invention is 20 parts by mass or less per 100 parts by mass of the polymerizable monomer blended into the adhesive composition of the present invention, which makes it easy to ensure operability and is also excellent in terms of cost.

The adhesive composition of the present invention for biological hard tissues used as a biological hard tissue coating material or biological hard tissue sealing material (in particular, a dental coating material or a dental sealing material) In addition to the polymer, the polyrotaxane of the present invention, and the polymerization initiator, other components can be further blended as necessary. For example, the adhesive composition of the present invention, which is used as a coating material for biological hard tissues or a sealing material for biological hard tissues (in particular, a dental coating material or a dental sealing material), is suitable for use in water ( Usually 1 to 200 parts by mass per 100 parts by mass of the polymerizable monomer to be blended in the adhesive composition of the present invention), organic solvent (polymerizable monomer to be blended in the adhesive composition of the present invention) (usually 5 to 800 parts by mass per 100 parts by mass), strength modifiers such as polymerization inhibitors or inorganic particles or organic particles such as silica or fumed silica (polymerizable to be blended in the adhesive composition of the present invention) (usually 1 to 50 parts by weight per 100 parts by weight of the monomer) may be added as necessary.

- Layer forming material for biological hard tissue or adhesive layer forming material for biological hard tissue (especially dental layer forming material or dental adhesive layer forming material) -
A layer-forming material for biological hard tissues or an adhesive layer-forming material for biological hard tissues (in particular, a dental layer-forming material or a dental adhesive layer-forming material (a dental adhesive layer-forming material is used as a dental bonding material) The adhesive composition of the present invention, which is used as a biological hard tissue, has adhesive properties to biological hard tissues such as bones, nails, teeth, etc., and is hardened by polymerization. An adhesive layer can be formed on the adhesion surface of the biological hard tissue.

The adhesive composition of the present invention, which is for biological hard tissues, is used as a biological hard tissue layer forming material or a biological hard tissue adhesive layer forming material (in particular, a dental layer forming material or a dental adhesive layer forming material) When an adhesive layer is formed on the adhesion surface of biological hard tissue, another curable material is generally adhered onto the adhesive layer. For example, since the adhesive layer has a surface unpolymerized layer, if another material (polymerizable curable material) that is polymerized and hardened using this surface unpolymerized layer is polymerized and hardened, the adhesive layer The polymeric curable material cures and adheres to the layer as a unit. In addition, the adhesive composition of the present invention for biological hard tissue may be used as a biological hard tissue layer forming material or a biological hard tissue adhesive layer forming material (in particular, a dental layer forming material or a dental adhesive layer forming material). When used as an adhesive layer to form an adhesive layer on the adhering surface of biological hard tissue, another material that hardens (hardenable material) is applied and hardened by another adhesive development mechanism. You can.

The amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention for biological hard tissues used as a layer forming material for biological hard tissues or an adhesive layer forming material for biological hard tissues (particularly a dental layer forming material or a dental adhesive layer forming material) is preferably within the range of 0.5 parts by mass to 500 parts by mass, more preferably within the range of 1 part by mass to 250 parts by mass, and most preferably within the range of 3 parts by mass to 200 parts by mass, relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. If the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention is less than 0.5 parts by mass relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the adhesive layer may not be sufficiently weakened after the structure of the polyrotaxane of the present invention is decomposed. Furthermore, if the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention exceeds 500 parts by mass per 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the viscosity may become too high, which may affect the operability of the layer-forming material for biological hard tissue or the adhesive layer-forming material for biological hard tissue (particularly the dental layer-forming material or dental adhesive layer-forming material).

Further, the adhesive properties of the present invention for biological hard tissue used as a biological hard tissue layer forming material or biological hard tissue adhesive layer forming material (in particular, a dental layer forming material or a dental adhesive layer forming material) When a polymerization initiator is blended into the composition, polymerization occurs quickly and cures under relatively mild conditions, so it is suitable, and the amount of the polymerization initiator blended into the adhesive composition of the present invention is suitable. It is preferably within the range of 0.001 parts by mass to 20 parts by mass, more preferably within the range of 0.005 parts by mass to 15 parts by mass, with respect to 100 parts by mass of the polymerizable monomer. Most preferably, it is within the range of .01 parts by weight to 10 parts by weight. The amount of the polymerization initiator blended in the adhesive composition of the present invention is 0.001 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. This makes it possible to improve the curability during polymerization. Furthermore, the amount of the polymerization initiator blended in the adhesive composition of the present invention is 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. This makes it easy to ensure operability and is also cost effective.

The adhesive composition of the present invention for biological hard tissues used as a biological hard tissue layer forming material or biological hard tissue adhesive layer forming material (particularly, a dental layer forming material or a dental adhesive layer forming material) In addition to the polymerizable monomer, the polyrotaxane of the present invention, and the polymerization initiator, other components may be further blended as necessary, such as water (usually 1 to 200 parts by weight per 100 parts by weight of the polymerizable monomer), organic solvent (usually 5 to 800 parts by weight per 100 parts by weight of the polymerizable monomer to be blended in the adhesive composition of the present invention) parts), polymerization inhibitors, or strength modifiers such as inorganic particles or organic particles such as silica or fumed silica (usually 1 part by mass for 100 parts by mass of the polymerizable monomer to be blended in the adhesive composition of the present invention). ~50 parts by mass) may be added as necessary.

- Dental adhesive resin cement -
The adhesive composition of the present invention for biological hard tissue may be used as a dental adhesive resin cement. Here, the dental adhesive resin cement may be a self-adhesive resin cement, or may be a dental adhesive resin cement kit in which the dental adhesive resin cement is combined with a dental adhesive primer described below. When the adhesive composition of the present invention for biological hard tissue is used as a dental adhesive resin cement kit in which the dental adhesive resin cement is combined with a dental adhesive primer, both or either one of the dental adhesive resin cement and the dental adhesive primer may contain the polymerizable monomer contained in the adhesive composition of the present invention, and both or either one of the dental adhesive resin cement and the dental adhesive primer may contain the polyrotaxane of the present invention.

The amount of the polyrotaxane of the present invention to be blended in the adhesive composition of the present invention for biological hard tissues used as a dental adhesive resin cement is preferably within the range of 1 part by mass to 250 parts by mass, more preferably within the range of 3 parts by mass to 150 parts by mass, and most preferably within the range of 5 parts by mass to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. If the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention is less than 1 part by mass relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the adhesive layer may not be sufficiently weakened after the polyrotaxane structure is decomposed. In addition, if the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention exceeds 100 parts by mass relative to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, the operability of the dental adhesive resin cement may be affected.

In addition, the amount of the polymerization initiator to be blended in the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissues, is It is preferably within the range of 0.001 parts by mass to 20 parts by mass, more preferably within the range of 0.005 parts by mass to 15 parts by mass, and 0.01 parts by mass with respect to 100 parts by mass of the polymer. Most preferably, the amount is within the range of 10 parts to 10 parts by weight. The amount of the polymerization initiator blended in the adhesive composition of the present invention is 0.001 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. This facilitates polymerization and curing. Furthermore, the amount of the polymerization initiator blended in the adhesive composition of the present invention is 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention. This makes it easy to ensure operability and is also cost effective. In addition, when the adhesive composition of the present invention, which is used for biological hard tissue, is used as a dental adhesive resin cement, a chemical polymerization initiator and a photopolymerization initiator are used in combination to make it a dual-cure type. You can.

The adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissue, contains other components as necessary in addition to the polymerizable monomer, the polyrotaxane of the present invention, and a polymerization initiator. can be further blended. For example, the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissue, may contain fillers such as the above-mentioned organic particles and inorganic particles, water, a polymerization inhibitor, an ultraviolet absorber, or an ultraviolet absorber. A sulfur compound or the like may be added as necessary. In particular, the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissues, can be prepared by adding fillers such as organic particles and inorganic particles. It is possible to ensure the mechanical strength of the cured product and further improve the operability. The amount of the filler to be blended in the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissue, is 100% of the polymerizable monomer blended in the adhesive composition of the present invention. It is preferably within the range of 1 part by mass to 250 parts by mass, more preferably within the range of 3 parts by mass to 150 parts by mass, and within the range of 5 parts by mass to 100 parts by mass. Most preferably. In addition, the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissue, has the effect of increasing the demineralization ability of tooth substance and the ability to penetrate into the tooth substance by adding water. Since it can be expected to have the effect of increasing the strength of the tooth, it can increase the adhesive strength to the tooth structure. The amount of water blended into the adhesive composition of the present invention for biological hard tissue used as a dental adhesive resin cement is 100 mass of the polymerizable monomer blended into the adhesive composition of the present invention. It is preferably within the range of 0.1 parts by mass to 15 parts by mass, more preferably within the range of 0.5 parts by mass to 10 parts by mass, and 1 part by mass to 7 parts by mass. Most preferably within this range.

The adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissues, is usually composed of the first component and the second component during storage, and is used by mixing the first component and the second component when in use. Here, the form of the first component and the second component may be either liquid or paste, but it is usually particularly preferable that both are paste-like.

As mentioned above, the adhesive composition of the present invention, which is used as a dental adhesive resin cement for biological hard tissues, is composed of the first component and the second component when stored, and the first component and the second component when used. When used in combination with a second component, each constituent material constituting the adhesive composition of the present invention is a mixture in which all constituent materials are a mixture of the first component and the second component. It is sufficient if it is included in the state of . That is, the first component may include some types of constituent materials among all types of constituent materials constituting the adhesive composition of the present invention, or may include all types of constituent materials. This point also applies to the second component. Furthermore, similarly, when the adhesive composition of the present invention is composed of a first component and a second component during storage, and when used by mixing the first component and second component, The amount of each constituent material constituting the adhesive composition of the present invention may be satisfied as long as it is in the state of a mixture of the first component and the second component. In this case, when the adhesive composition of the present invention is used as a dental adhesive resin cement, the blending amount of each constituent material is determined by mixing the first component and the second component as determined in advance. It means the amount when mixed according to the ratio (mixing ratio in use). Here, the "mixing ratio for use" refers to the use manual or product manual of the commercial product when the adhesive composition of the present invention is a commercial product sold as a dental adhesive resin cement. etc. (mixing ratio recommended by the manufacturer or distributor). In addition to information on the mixing ratio for use, in addition to what is written in the instruction manual or product manual attached to the product, information on the mixing ratio may also be provided by mail, email, or information provided by the manufacturer. It may be provided on the web page of the seller.

-Dental adhesive primer-
The adhesive composition of the present invention, which is intended for biological hard tissue, can be used as a dental adhesive primer (self-etching primer). The adhesive composition of the present invention, which is used as a dental adhesive primer for biological hard tissue, forms a primer layer by polymerizing and curing.

The amount of the polyrotaxane of the present invention blended into the adhesive composition of the present invention, which is used as a dental adhesive primer for biological hard tissue, is the same as the amount of the polymerizable monomer blended into the adhesive composition of the present invention. With respect to 100 parts by mass, it is preferably within the range of 1 part by mass to 250 parts by mass, more preferably within the range of 3 parts by mass to 150 parts by mass, and within the range of 5 parts by mass to 100 parts by mass. Most preferably. When the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention is less than 1 part by mass with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, After decomposition of the structure of the polyrotaxane of the present invention, the weakening of the primer layer may be insufficient. Furthermore, if the amount of the polyrotaxane of the present invention blended in the adhesive composition of the present invention exceeds 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer blended in the adhesive composition of the present invention, , the operability of the primer may be affected.

The adhesive composition of the present invention, which is used as a dental adhesive primer for biological hard tissue, contains fillers such as the above-mentioned organic particles and inorganic particles, water, a polymerization inhibitor, an ultraviolet absorber, a sulfur-containing compound, etc. may be added as necessary. In particular, the adhesive composition of the present invention, which is used as a dental adhesive primer for biological hard tissue, has the effect of increasing the demineralization ability of tooth substance and the permeability into tooth substance by adding water. It can be expected to have the effect of increasing the adhesive strength to the tooth structure. The amount of water blended into the adhesive composition of the present invention for biological hard tissue used as a dental adhesive primer is 100 parts by mass of the polymerizable monomer blended into the adhesive composition of the present invention. It is preferably within the range of 1 part by mass to 200 parts by mass, more preferably within the range of 5 parts by mass to 180 parts by mass, and preferably within the range of 10 parts by mass to 150 parts by mass. is most preferred.

Example 1: Synthesis of 7-diethylaminocoumarin-blocked polyrotaxane 16.9 g of α-cyclodextrin was measured and dissolved in 116.1 mL of ultrapure water. 3.38 g of PEG (number average molecular weight 10,000) having amino groups at both ends was measured and dissolved in 13.5 mL of ultrapure water. The PEG aqueous solution was added dropwise to the α-cyclodextrin aqueous solution, and the mixture was stirred at room temperature for 24 hours. The precipitate produced by the reaction was collected by centrifugation and freeze-dried for 2 days to obtain 14.6 g of pseudopolyrotaxane. Pseudo-polyrotaxane was added to an eggplant-shaped flask, and pressure reduction and nitrogen addition were repeated to replace the interior of the reaction vessel with nitrogen. Weigh out 1.39 g of (7-diethylaminocoumarin-4-yl)methyl 4-nitrophenyl carbonate into another eggplant-shaped flask, and add 100 mL of dehydrated N,N-dimethylformamide and N,N-diisopropylethylamine under a nitrogen atmosphere. 5.85 mL was added and dissolved. This solution was added to the pseudopolyrotaxane under a nitrogen atmosphere, and the mixture was stirred at room temperature for 24 hours while shielded from light. After the reaction, the precipitate was collected by centrifugation. Dimethyl sulfoxide was added to the precipitate and stirred, ultrapure water was added and centrifuged, and the precipitate was collected again. By repeating this operation, unreacted substances and free α-cyclodextrin were removed. The precipitate was freeze-dried to obtain 8.37 g of 7-diethylaminocoumarin-blocked polyrotaxane (hereinafter abbreviated as PRX-DEACM). The yield calculated in terms of polyethylene glycol moles was 47.2%.
Since the polyrotaxane of Example 1 has a 7-diethylaminocoumarin derivative introduced as a blocking group, only the product blocked with the 7-diethylaminocoumarin derivative can be recovered. The introduction rate is theoretically 100%.
Figure 1 shows the results of measuring the nuclear magnetic resonance spectrum ( ¹ H NMR) of PRX-DEACM in dimethyl sulfoxide (hereinafter abbreviated as DMSO) _-d6 using Avance III 400 MHz (manufactured by Bruker BioSpin). be. From the results shown in Figure 1, peaks derived from the aromatic ring of the 7-diethylaminocoumarin derivative, which is a photodegradable group, were observed at 6.55, 6.70, and 7.44 ppm, confirming its introduction into polyrotaxane. It was confirmed that the introduction rate was approximately 100%.
In this way, the polyrotaxane of Example 1 was able to introduce photodegradable groups with high efficiency.
Further, the α-cyclodextrin penetration number of PRX-DEACM calculated from the ¹ H NMR spectrum was 43.7, and the number average molecular weight was 53,000.

Example 2: Synthesis of photodegradable PRX-DEACM crosslinking agent 4.0 g of PRX-DEACM was weighed into an eggplant-shaped flask and replaced with nitrogen. 70 mL of dehydrated dimethyl sulfoxide was added to this flask under a nitrogen atmosphere to dissolve PRX-DEACM. 1.48 g of 1,4-diazabicyclo[2.2.2]octane was weighed into another eggplant-shaped flask, and the flask was purged with nitrogen. 10 mL of dehydrated dimethyl sulfoxide was added to the flask under a nitrogen atmosphere. Add 1,4-diazabicyclo[2.2.2]octane solution, 0.465 mL of 2-isocyanatoethyl methacrylate, and 9.18 mL of butyl isocyanate to the PRX-DEACM solution, and stir at room temperature for 24 hours in the dark. did. After the reaction, dialysis was performed against dimethyl sulfoxide for 2 days and against ultrapure water for 2 days using a dialysis membrane with a molecular weight cut off of 3500. The precipitate was collected and freeze-dried to obtain 6.60 g of a PRX-DEACM crosslinking agent modified with a methacryloyl group and an n-butyl group (hereinafter abbreviated as MB-PRX-DEACM). The yield was 77.9%.
The number of methacryloyl group modifications in MB-PRX-DEACM calculated from the ¹ H NMR spectrum was 38.3, the number of n-butyl group modifications was 446, and the number average molecular weight was 103,000.
As described above, the polyrotaxane of Example 2 required only three steps from the synthesis of the polyrotaxane to the synthesis of the crosslinkable modified product, and could be easily synthesized.

Reference Example 1: Synthesis of non-degradable adamantane-blocked polyrotaxane A pseudopolyrotaxane was prepared in the same manner as in Example 1, and added to an eggplant-shaped flask. 1.42 g of 1-adamantanecarboxylic acid and 3.48 g of BOP reagent were added to another eggplant-shaped flask and dissolved in 120 mL of dehydrated N,N-dimethylformamide. 1.35 mL of N,N-diisopropylethylamine was added to the flask and stirred. This solution was added to pseudopolyrotaxane and stirred at room temperature for 24 hours. After the reaction, the precipitate was collected by centrifugation. Dimethyl sulfoxide was added to the precipitate and stirred, ultrapure water was added and centrifuged, and the precipitate was collected again. By repeating this operation, unreacted substances and free α-cyclodextrin were removed. The precipitate was freeze-dried to obtain 8.36 g of adamantane-blocked polyrotaxane (hereinafter abbreviated as PRX-Ad). The yield calculated in terms of polyethylene glycol moles was 38.0%.
The α-cyclodextrin penetration number of PRX-Ad calculated from the ¹ H NMR spectrum was 47.2, and the number average molecular weight was 56,200.

Reference Example 2: Synthesis of non-degradable PRX-Ad crosslinking agent 1.0 g of PRX-Ad was weighed out in an eggplant-shaped flask and nitrogen substitution was performed. 18 mL of dehydrated dimethyl sulfoxide was added to this flask under a nitrogen atmosphere to dissolve PRX-Ad. 0.38 g of 1,4-diazabicyclo[2.2.2]octane was weighed out in another eggplant-shaped flask and nitrogen substitution was performed. 2 mL of dehydrated dimethyl sulfoxide was added to this flask under a nitrogen atmosphere. 1,4-diazabicyclo[2.2.2]octane solution, 0.118 mL of 2-isocyanatoethyl methacrylate, and 2.34 mL of butyl isocyanate were added to the PRX-Ad solution in order, and the mixture was stirred at room temperature for 24 hours in the dark. After the reaction, the mixture was dialyzed against dimethyl sulfoxide for 2 days using a dialysis membrane with a molecular weight cutoff of 3500, and against ultrapure water for 2 days. The precipitate was collected and freeze-dried to obtain 1.54 g of a PRX-Ad crosslinking agent modified with a methacryloyl group and an n-butyl group (hereinafter abbreviated as MB-PRX-Ad). The yield was 87.1%.
The number of methacryloyl modifications in MB-PRX-Ad calculated from the ¹ H NMR spectrum was 18.4, the number of n-butyl modifications was 403, and the number average molecular weight was 99,000.

Comparative example 1
According to a previous report (ACS Macro Letters 2015, 4, 1154-1157), 4-(bromomethyl)-3-nitrobenzoic acid was reacted with sodium carbonate at 60°C for 2 hours to produce 4-hydroxymethyl-3-nitrobenzoic acid. Synthesize this and polyethylene glycol (number average molecular weight 10,000) having amino groups at both ends with 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride. was introduced into both ends of polyethylene glycol by reacting at room temperature for 24 hours in the presence of. This was reacted with 4-nitrophenyl chloroformate overnight, and then reacted with ethylenediamine for 24 hours at room temperature to obtain polyethylene glycol having nitrobenzyl groups introduced at both ends. The product and α-cyclodextrin were reacted in distilled water at room temperature for 24 hours, and the product was freeze-dried to obtain a pseudopolyrotaxane. Pseudopolyrotaxane and N-benzyloxycarbonyl-L-tyrosine were treated in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride at room temperature for 24 hours. By the reaction, the desired polyrotaxane having nitrobenzyl groups at both ends (hereinafter abbreviated as PRX-NB) was obtained.
Next, the introduction rate of the nitrobenzyl group, which is a photodegradable group, in the polyrotaxane of Comparative Example 1 was examined by ¹ H NMR method, and was found to be about 70%.
Next, PRX-NB (hereinafter abbreviated as MB-PRX-NB) in which the methacryloyl group and n-butyl group were chemically modified was synthesized using the same procedure as in Reference Example 1.
As described above, the polyrotaxane of Comparative Example 1 required eight steps from the synthesis of the polyrotaxane to the synthesis of the crosslinkable modified product.

Comparative example 2
According to a previous report (ACS Applied Pokymer Materials 2020, 2, 5756-5766), 2-nitro-p-xylylene glycol and 1,1'-carbonyldiimidazole were activated by reacting at room temperature for 2 hours. The product was reacted with polyethylene glycol (number average molecular weight 10,000) having amino groups at both ends in tetrahydrofuran at room temperature for 24 hours to increase the amount of the product. Thereafter, the monomer was removed by dialysis, and only the multimer was recovered. A polyethylene glycol polymer containing a nitrobenzyl group was reacted with α-cyclodextrin in distilled water at room temperature for 24 hours, and the product was freeze-dried to obtain a pseudopolyrotaxane. By reacting pseudopolyrotaxane and 1-carboxyadamantane at room temperature for 24 hours in the presence of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, The desired polyrotaxane (hereinafter abbreviated as iNB-PRX) having a nitrobenzyl group in the axial polymer was obtained.
Next, the introduction rate of the nitrobenzyl group, which is a photodegradable group, in the polyrotaxane of Comparative Example 2 was examined by ¹ H NMR, and was found to be about 90%.
Next, in the same manner as in Reference Example 1, iNB-PRX (hereinafter abbreviated as MB-iNB-PRX) in which the methacryloyl group and n-butyl group were chemically modified was synthesized.
As described above, the polyrotaxane of Comparative Example 2 required five steps from the synthesis of the polyrotaxane to the synthesis of the crosslinkable modified product.

Test example 1
The polyrotaxane crosslinking agents of Example 2 and Comparative Example 1 were dissolved in acetonitrile, and the absorption spectra were measured using a spectrophotometer V-550 (manufactured by JASCO Corporation).
The results are shown in Figure 2. As shown in FIG. 2, the photodegradable polyrotaxane crosslinking agent (MB-PRX-DEACM) of Example 2 exhibited absorption at 376 nm derived from 7-diethylaminocoumarin. On the other hand, the maximum absorption wavelength of the photodegradable polyrotaxane crosslinking agent (MB-PRX-NB) of Comparative Example 1 is 271 nm. Thus, the polyrotaxane of Example 2 requires a longer wavelength of light for decomposition than the polyrotaxane of Comparative Example 1.

Test Example 2
The polyrotaxane crosslinking agents of Example 2 and Comparative Example 1 were dissolved in dimethyl sulfoxide and irradiated with visible light having a wavelength of 465 nm (light source: Moritex Corp. MDBL-CB100, maximum wavelength 465 nm, irradiance 44.5 mW/cm ² ) or near-ultraviolet light having a wavelength of 365 nm (light source: Moritex Corp. MBRL-CUV7530-2, maximum wavelength 365 nm, irradiance 7.03 mW/cm ² ), and the change over time in the amount of each polyrotaxane was confirmed by GPC. The decomposition rate of the polyrotaxane was quantified from the peak area obtained by an ultraviolet-visible absorption detector.
The results are shown in Figure 3. As shown in Figure 3, the photodegradable polyrotaxane crosslinking agent of Example 2 (MB-PRX-DEACM) was hardly decomposed by irradiation with visible light having a wavelength of 465 nm, but was almost completely decomposed by irradiation with near-ultraviolet light having a wavelength of 365 nm for 20 minutes. This is in contrast to the photodegradable polyrotaxane crosslinking agent of Comparative Example 1 (MB-PRX-NB), which was only decomposed by about 40% even after 60 minutes by irradiation with near-ultraviolet light having a wavelength of 365 nm. Thus, the polyrotaxane of Example 1 was decomposed even by irradiation with ultraviolet light having a relatively high wavelength and low toxicity.

Test example 3
10% by weight of the photodegradable polyrotaxane crosslinking agent (MB-PRX-DEACM) of Example 2 as a crosslinking agent, 88% by weight of 2-hydroxyethyl methacrylate (HEMA), and camphorquinone and diethylaminoethyl methacrylate as initiators. 1% by weight of each was mixed, poured into a PTFE mold (JIS 7 type, thickness 0.5mm), irradiated with visible light (light source: MDBL-CB100 manufactured by Moritex) for 2 minutes to cause polymerization, and then overnight. A cured product was obtained by allowing it to stand still.
A cured product of Reference Example 2 was also obtained by the same method using the non-degradable polyrotaxane crosslinking agent (MB-PRX-Ad) of Reference Example 2.
The maximum tensile stress (breaking strength) of each of the cured product of Example 2 and the cured product of Reference Example 2 was examined by a tensile test method. The tensile test was evaluated using EZ-SX (manufactured by Shimadzu Corporation), and the maximum tensile stress was calculated from the area of the fracture surface.
The results are shown in Figure 4. As shown in FIG. 4, the maximum tensile stress (breaking strength) of the cured product of Reference Example 2 did not change significantly even after 5 minutes of irradiation with near-ultraviolet light with a wavelength of 365 nm. In the cured product of No. 1, the tensile stress significantly decreased by about 50% by irradiation with near-ultraviolet light having a wavelength of 365 nm for 5 minutes.
As described above, conventionally, it was necessary to irradiate light with a wavelength of 254 nm, which has a higher energy, but the cured product obtained by polymerizing the polymerizable monomer in the presence of the polyrotaxane of Example 2 has a relatively high energy It was found that it was decomposed by irradiation with ultraviolet light, which has a wavelength of low toxicity.

Claims (7)

A polyrotaxane having a cyclic molecule, an axial molecule that passes through the cyclic molecule, and a blocking group that is disposed on the axial molecule and prevents the cyclic molecule from being detached, the blocking group including a coumarin derivative. An adhesive composition comprising the polyrotaxane according to claim 1 and a polymerizable monomer. The adhesive composition according to claim 2, which is used for biological hard tissue. The adhesive composition according to claim 3, characterized in that it is used for dentistry. The adhesive composition according to claim 4, characterized in that it is used for bonding orthodontic brackets or for temporary attachment of implants. An adhesive comprising the adhesive composition according to any one of claims 2 to 5. A method for reducing the mechanical strength of a cured product of the adhesive composition according to any one of claims 2 to 5, comprising the step of irradiating the cured product with ultraviolet light.