JP2005146120A - Method for introducing alkoxysilyl group, introduced material, method for producing complex by using the same and complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for introducing an alkoxysilyl group in which the alkoxysilyl group is introduced into a base material in an aqueous solvent without modifying properties of the base material. <P>SOLUTION: The method for introducing the alkoxysilyl group comprises a protective step for protecting an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant, and an introduction step for introducing the alkoxysilyl group into the base material by reacting the reactive functional group of the protected alkoxysilyl group-containing compound protected by the protective step with a base material capable of reacting with the reactive functional group in an aqueous solvent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an alkoxysilyl group introduction method for introducing an alkoxysilyl group onto a substrate surface using a silane coupling agent in an aqueous solvent, and an introduced product obtained by the above alkoxysilyl group introduction method In addition, the present invention relates to a production method and a composite for producing a composite using the above alkoxysilyl group introduction method.

  A silane coupling agent is a compound that combines a part that is reactive to an inorganic substance and a part that is highly reactive and soluble in an organic substance in one molecule. For example, it acts as a cross-linking agent at the interface between an inorganic substance and an organic substance. Because of this, it is used in many composite materials. Silane coupling agents are also used as modifiers for modifying the properties of organic and inorganic material surfaces.

  Conventionally, as a production method for producing a composite composed of two substrates using a silane coupling agent, for example, three methods of an integral blend method, a dry treatment method, and a wet treatment method are known.

  The integral blend method is a method of adding a silane coupling agent to an organic material when mixing the inorganic material and the organic base material. Since it can be compounded in one stage, it is often used industrially, but has the disadvantage that uniform processing is difficult.

  The dry processing method is a method in which a filler is charged into a machine capable of high-speed stirring such as a Henschel mixer and a silane coupling agent or a hydrolyzed solution of the silane coupling agent is added dropwise under stirring. This dry processing method has many advantages such as processing a large amount of filler in a short time and requiring a heat source not so much for processing. However, uniform processing is difficult as with the integral blend method. Moreover, as a method for improving this point, for example, Patent Publication 1 is disclosed. The patent publication 1 describes a method of surface treatment with a gaseous silane coupling agent. However, in the method disclosed in Patent Document 1, it is necessary to heat the silane coupling agent, and since the boiling point of the silane coupling agent is generally high, a large amount of heat source is required.

The wet processing method is a method of processing in a solution in which a filler and a silane coupling agent are dissolved in a hydrolysis solvent (usually water, alcohol, or a mixed solvent thereof). An example of the wet processing method is disclosed in Patent Document 2. Patent Document 2 describes a method in which a silane coupling agent is added to water and treated with a treatment liquid obtained by hydrolysis. However, this wet processing method is industrially disadvantageous because it requires a heat source at the time of drying, and contributes to bonding on the surface of filler particles because of insufficient hydrolysis of the silane coupling agent on the filler surface. It has been found that no hydrolyzable groups remain.
Japanese Patent Laid-Open No. 5-86265 (Release Date; April 6, 1993) JP 4-108853 A (publication date; April 2, 1992)

  In the above three methods, the substrate surface is modified with an alkoxysilyl group or a hydroxysilyl group of a silane coupling agent. That is, in the above conventional method, the alkoxysilyl group or hydroxysilyl group is reacted with the substrate. For this reason, since an alkoxysilyl group or a hydroxysilyl group reacts, an alkoxysilyl group or a hydroxysilyl group cannot be introduced on the surface of the substrate.

  Moreover, when a silane coupling agent containing an alkoxysilyl group or a hydroxysilyl group is introduced into water, hydrolysis is promoted, and the alkoxysilyl group or hydroxysilyl group reacts to form a siloxane bond. For this reason, when introducing an alkoxysilyl group or a hydroxysilyl group into a substrate, it is necessary to introduce it in an anhydrous solvent (in a water-free solvent).

  Furthermore, in the above conventional method, a silane coupling agent is used for the purpose of modifying the base material, and there is a problem that the properties of the base material are altered even when a composite is produced. That is, for example, even when it is desired to use the inherent property of the base material, when the composite is produced using the silane coupling agent, the inherent property of the base material is impaired.

  The present invention has been made in view of the above problems, and an object of the present invention is to introduce an alkoxysilyl group introduction method for introducing an alkoxysilyl group into a base material in an aqueous solvent without modifying the properties of the base material. And an introduced product obtained by this alkoxysilyl group introduction method, a production method for producing a composite using the above alkoxysilyl group introduction method, and a composite.

  In order to solve the above-mentioned problems, the alkoxysilyl group introduction method according to the present invention protects an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant, and the protection step Introduction of introducing an alkoxysilyl group into a base material by reacting a reactive functional group of a protected alkoxysilyl group-containing compound protected by the above and a base material capable of reacting with the reactive functional group in an aqueous solvent And a process.

  In the alkoxysilyl group introduction method according to the present invention, the base material preferably has a functional group capable of reacting with a reactive functional group on the surface of the base material.

  In addition, the alkoxysilyl group introduction method according to the present invention more preferably includes a functional group introduction step of introducing a functional group capable of reacting with the reactive functional group into the substrate before the introduction step.

  In order to solve the above problems, the alkoxysilyl group introduction method according to the present invention is characterized in that an alkoxysilyl group is introduced onto the surface of a substrate by the above alkoxysilyl group introduction method.

  Moreover, the alkoxysilyl group introduction method according to the present invention preferably has a configuration in which the substrate is silk fibroin.

  In order to solve the above problems, the method for producing a composite according to the present invention includes a protection step of protecting an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant, and the protection step. Introduction step of introducing an alkoxysilyl group into a base material by reacting the reactive functional group of the protected alkoxysilyl group-containing compound protected by the above and a base material capable of reacting with the reactive functional group in an aqueous solvent And a reaction step of reacting an alkoxysilyl group introduced into the substrate and a reactive substrate capable of reacting with the alkoxysilyl group.

  Moreover, as for the manufacturing method of the composite_body | complex which concerns on this invention, the structure in which the said base material has a functional group which can react with a reactive functional group is more preferable.

  In addition, the method for producing a composite according to the present invention preferably includes a functional group introducing step of introducing a functional group capable of reacting with the reactive functional group into the substrate before the introducing step.

  Moreover, the manufacturing method of the composite_body | complex which concerns on this invention has a more preferable structure which has the reactive active group which can react with the said alkoxy silyl group on the surface of the said reactive base material.

  Moreover, the manufacturing method of the composite_body | complex which concerns on this invention has the structure including the reactive active group introduction | transduction process which introduce | transduces the reactive active group which can react with the said alkoxy silyl group to the reactive base material before the said reaction process. More preferred.

  The composite production method according to the present invention more preferably includes a desorption step of desorbing the surfactant protecting the alkoxysilyl group-containing compound after the introduction step.

  The complex of the complex according to the present invention is characterized by being produced by the complex production method in order to solve the above problems.

  Moreover, the composite of the composite according to the present invention preferably has a configuration in which the base material is silk fibroin and the reactive base material is a hydroxyapatite sintered body.

  The introduction method according to the present invention includes a protection step for protecting an alkoxysilyl group-containing compound with a surfactant and an introduction step for introducing an alkoxysilyl group into a substrate.

  By setting it as the said structure, since the alkoxysilyl group containing compound containing an alkoxy silyl group is protected with surfactant, an alkoxy silyl group can be introduce | transduced into a base material even in an aqueous solvent. Moreover, since an alkoxysilyl group can be introduced in an aqueous solvent, the treatment of the solvent is simplified and the cost for the solvent can be reduced. Thus, by setting it as said structure, there exists an effect that an alkoxy silyl group can be introduce | transduced into a base material in an aqueous medium, without modifying the property of a base material.

  In the introduction method according to the present invention, the base material preferably has a functional group capable of reacting with a reactive functional group on the surface of the base material. According to said structure, since it has a functional group which can react with a reactive functional group, an alkoxysilyl group can be more reliably introduce | transduced into the surface of a base material.

  The introduction method according to the present invention more preferably includes a functional group introduction step of introducing a functional group capable of reacting with the reactive functional group into the base material before the introduction step. Thereby, since the said reactive group should just be introduce | transduced into a base material, the freedom degree of selection of a base material becomes high. That is, even when the substrate itself does not have the reactive group, an alkoxysilyl group can be introduced.

  The introduction according to the present invention has a structure in which an alkoxysilyl group is introduced onto the surface of a substrate by the above-described alkoxysilyl group introduction method. Therefore, various composites can be produced by reacting the alkoxysilyl group of the introduced product with another substrate.

  Moreover, as for the introduced substance which concerns on this invention, the structure whose said base material is silk fibroin is more preferable. According to said structure, since a base material is silk fibroin, a medical material with high biocompatibility can be provided by using a medical material for the other base material made to react with an alkoxy silyl group.

  The method for producing a composite according to the present invention includes a protection step for protecting an alkoxysilyl group-containing compound with a surfactant, an introduction step for introducing an alkoxysilyl group into the substrate, and an alkoxysilyl group introduced into the substrate. And a reaction step of reacting the reactive base capable of reacting with the alkoxysilyl group.

  According to said structure, the base material in which the alkoxy silyl group was introduce | transduced and the reactive base material can be chemically bonded in an aqueous solvent. Thereby, the safety | security at the time of using for the biomaterial of the composite_body | complex finally obtained can be made still higher, for example. Moreover, there exists an effect that a composite_body | complex can be manufactured in the state which maintained the property of base material itself.

  Moreover, as for the manufacturing method of the composite_body | complex which concerns on this invention, the structure in which the said base material has a functional group which can react with a reactive functional group is more preferable. According to said structure, since it has a functional group which can react with a reactive functional group, an alkoxysilyl group can be more reliably introduce | transduced into the surface of a base material.

  More preferably, the method for producing a composite according to the present invention includes a functional group introduction step of introducing a functional group into the substrate before the introduction step. Thereby, since the said functional group should just be introduced into a base material later, the freedom degree of selection of a base material becomes high. That is, an alkoxysilyl group can be introduced even when the substrate itself does not have the functional group.

  In the method for producing a composite according to the present invention, it is more preferable that the surface of the reactive substrate has a reactive active group capable of reacting with the alkoxysilyl group. According to said structure, since it has the reactive active group which can react with the alkoxy silyl group on the base-material surface, an alkoxy silyl group and a reactive base material can be combined more reliably.

  More preferably, the method for producing a complex according to the present invention includes a reactive active group introduction step of introducing a reactive active group into the reactive substrate before the reaction step. According to said structure, since the reactive active group is introduce | transduced later, the freedom degree which the reactive base material to use can be selected can be made high.

  More preferably, the method for producing a composite according to the present invention includes a desorption step of desorbing the surfactant protecting the alkoxysilyl group-containing compound after the introduction step. According to the above configuration, since the surfactant is removed, the complex can be produced under simpler reaction conditions.

  The composite according to the present invention has a configuration manufactured by the above-described composite manufacturing method. By setting it as said structure, the composite_body | complex which the base material and the reactive base material have not modified | denatured can be provided.

  The composite according to the present invention preferably has a configuration in which the base material is silk fibroin and the reactive base material is a hydroxyapatite sintered body. By setting it as said structure, a composite_body | complex with high biological activity can be provided.

  An embodiment of the present invention will be described as follows. That is, in the method for introducing an alkoxysilyl group according to the present embodiment, an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group is protected by a surfactant, and the alkoxysilyl group-containing compound in this protected state is protected. In this method, an alkoxysilyl group is introduced into a substrate by reacting the reactive functional group with a substrate capable of reacting with the reactive functional group.

  Moreover, the manufacturing method of the composite_body | complex concerning this Embodiment is the reactive base material which can react with the alkoxysilyl group introduce | transduced into the said base material after performing the said introduction method, and the said alkoxysilyl group. This is a reaction method.

(Alkoxysilyl group-containing compound)
The alkoxysilyl group-containing compound according to the present embodiment refers to a compound having at least an alkoxysilyl group and a reactive functional group.

The alkoxysilyl group refers to a group containing Si—OR. That is, in this embodiment, the alkoxysilyl group includes ≡Si—OR, ═Si— (OR) ₂ , —Si— (OR) _{3, and the} like. The above ≡ and = do not indicate only a triple bond or a double bond, and each bond may be bonded to a different group. Accordingly, for example, —SiH— (OR) ₂ , —SiH ₂ — (OR) and the like are also included in the alkoxysilyl group. And R of said Si-OR has shown the alkyl group or hydrogen. That is, in this embodiment, the hydroxysilyl group is also a kind of alkoxysilyl group. As the alkyl group, a methyl group, an ethyl group, or the like can be preferably used.

  Specific examples of the alkoxysilyl group-containing compound include silane coupling agents. Here, the silane coupling agent will be described.

  The silane coupling agent has a chemical structure as shown in chemical formula (1).

Z-Si≡ (OR) ₃ (1)
Z may be any reactive functional group that can chemically bond to organic materials (for example, polymer base materials) such as various synthetic resins. Specifically, for example, vinyl group, epoxy group, amino group , (Meth) acryloxy group, mercapto group and the like. The OR may be any material that can be chemically bonded to an inorganic material (hydroxyapatite sintered body), and specific examples thereof include a methoxy group and an ethoxy group. In addition, about three OR in the said Chemical formula (1), they may be the same and may differ. And Si-OR of the said Chemical formula (1) is an alkoxy silyl group. In addition, the reactive functional group Z and Si in the chemical formula (1) may be bonded via a polymer chain or may be bonded via a low molecular chain, for example. It may be combined.

  That is, as the silane coupling agent, specifically, for example, vinyl silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane; β- (3,4 epoxycyclohexyl) ethyltri Epoxy silane coupling agents such as methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane; p-styryltrimethoxysilane, etc. Stylyl-based silane coupling agents; methacrylic compounds such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane Roxy-based silane coupling agents; acryloxy-based silane coupling agents such as γ-acryloxypropyltrimethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Methyldimethoxymethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-triethoxy-N- (1,3-dimethyl-butylidene ) Amino-based silane coupling agents such as propylamine, N-phenyl-γ-aminopropyltrimethoxysilane, N- (vinylbenzyl) -β-aminoethyl-γ-aminopropyltrimethoxysilane hydrochloride, special aminosilane; γ-ureidopropyltriethoxysila Ureido silane coupling agents such as chlorosilanes; Chloropropyl silane coupling agents such as γ-chloropropyltrimethoxysilane; Mercapto silane coupling agents such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane A sulfide-based silane coupling agent such as bis (triethoxypropyl) tetrasulfide; an isocyanate-based silane coupling agent such as γ-isocyanatopropyltriethoxysilane; Of the silane coupling agents exemplified above, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are more preferable because they are polymerizable monomers. The silane coupling agent is appropriately selected depending on the type of the polymer substrate and, when a reactive active group (described later) is introduced on the surface of the polymer substrate, the type of the reactive active group, etc. do it.

(Base material)
The said base material can react with the reactive functional group which the alkoxy silyl group containing compound has. Specifically, the base material may have a functional group capable of reacting with the reactive function. Further, for example, the substrate surface may be directly reacted with the reactive functional group by subjecting the substrate surface to corona treatment. In addition, when the said base material contains a functional group, the said functional group may be introduce | transduced by performing a functional group introduction | transduction process to a base material, and the base material itself has a functional group. It may be a thing. The functional group introduction step will be described later.

  Specific examples of the substrate include organic polymer substrates, and more specifically, silicone polymers (which may be silicone rubber), polyethylene glycol, polyalkylene glycol, and polyglycolic acid. , Polylactic acid, polyamide, polyurethane, polysulfone, polyether, polyetherketone, polyamine, polyurea, polyimide, polyester, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylic acid, polymethacrylic acid, polymethylmethacrylate, polyacrylonitrile Synthetic polymers such as polystyrene, polyvinyl alcohol and polyvinyl chloride; polysaccharides such as cellulose, amylose, amylopectin, chitin and chitosan, polypeptides such as collagen, hyaluronic acid, chondroitin, Chondroitin mucopolysaccharides such as sulfuric, natural polymers, and the like silk fibroin and the like. Of the above-exemplified base materials, silicone polymer, polyurethane, polytetrafluoroethylene, or silk fibroin is preferably used because it has excellent properties such as long-term stability, strength, and flexibility.

  And as for these base materials, a various thing can be selected according to a use. Specifically, when the composite produced using this base material is used as, for example, a medical material, the base material is a medical polymer material, and more specifically, silicone rubber or silk fibroin. It is more preferable to use fibers or the like.

  Further, instead of the above-exemplified base materials, specifically, for example, a base material of an inorganic material such as titanium oxide or a titanium alloy that can be suitably used as a medical material can be used. . Therefore, the base material according to the present invention includes a base material made of an inorganic material such as titanium oxide.

  In addition, the shape of the substrate may be, for example, a sheet shape, a fiber shape, a tube shape, or a porous body, and may be appropriately selected depending on the application.

(Surfactant)
The surfactant for protecting the alkoxysilyl group-containing compound varies depending on the type of the alkoxysilyl group-containing compound, and specifically, for example, pentaethylene glycol dodecyl ether, hexaethylene glycol monododecyl ether, nonylphenyl polyoxy Nonionic surfactants such as ethylene, polyoxyethylene (10) octylphenyl ether, dodecyl-β-glucoside and the like can be mentioned.

(Reactive substrate)
The said reactive base material is a thing which can react with the alkoxy silyl group which the alkoxy silyl group containing compound has. Specifically, the reactive substrate has a reactive active group capable of reacting with the alkoxysilyl group of the alkoxysilyl group-containing compound. This reactive active group may be one that the reactive substrate itself has, and is introduced by performing a reactive active group introduction step of introducing the reactive active group into the reactive substrate. It may be. The reactive active group introduction step will be described later.

  The reactive substrate is not particularly limited as long as it can react with an alkoxysilyl group, but in particular, a substrate having a hydroxyl group on the surface is more preferable. Moreover, as said reactive base material, you may have an amino group or an epoxy group on the surface. Therefore, as the reactive substrate, those having at least one kind of reactive active group of hydroxyl group, amino group, and epoxy group on the surface are more preferable.

  Specifically, examples of the reactive substrate include inorganic materials such as hydroxyapatite, titanium oxide, silica, and glass. In addition, as the reactive substrate, for example, copper, aramid, or the like can be used. Of the reaction base materials exemplified above, hydroxyapatite and titanium oxide having a hydroxyl group on the surface are particularly preferably used. Further, the hydroxyapatite and titanium oxide can be suitably used for medical materials. Therefore, when using the composite manufactured using the said reactive base material as a medical material, it is more preferable to use a hydroxyapatite or a titanium oxide as a reactive base material.

  The shape of the reactive base material varies depending on the application to be used. For example, when the shape of the base material is a sheet shape, a fiber shape, a tube shape, or a porous body, the shape of the reactive base material is excellent. In order to make it combine, it is more preferable that it is particulate. When the shape of the reactive base material is particulate, the size (particle diameter) is such that the reactive base material and the base material are chemically bonded to each other so that they can be fixed on the surface of the base material. Any diameter may be used. Specifically, the lower limit of the particle diameter is more preferably 0.001 μm or more, and further preferably 0.01 μm or more. When the particle diameter is smaller than 0.001 μm, the reactive base material and the base material may not be bonded with a desired strength, and the reactive base material may be detached from the base material. On the other hand, the upper limit of the particle diameter is more preferably 1000 μm or less, and even more preferably 100 μm or less. When the particle diameter is larger than 1000 μm, the bond between the reactive base material and the base material may be relatively weak.

(Alkoxysilyl group introduction method)
The alkoxysilyl group introduction method according to this embodiment will be described below. More specifically, a method of reacting a reactive functional group of the silane coupling agent with a polymer substrate using a silane coupling agent will be described. Specifically, the alkoxysilyl group introduction method includes a protection step and an introduction step performed in an aqueous solvent.

  (Protection Step) Here, the protection step will be described. In the protection step, the silane coupling agent is protected with a surfactant. Specifically, the silane coupling agent (the alkoxysilyl group and the reactive functional group of the silane coupling agent) is protected by mixing the silane coupling agent and the surfactant. In this protection step, the amount of the surfactant used is more preferably in the range of 1.0 to 50.0% by weight relative to the silane coupling agent, and the range of 10.0 to 25.0% by weight. The inside is more preferable. By using the surfactant within the above range, the alkoxysilyl group of the silane coupling agent can be reliably protected from water.

  The surfactant has a hydrophilic part and a lipophilic part (hydrophobic part). When the silane coupling agent is protected with a surfactant, the lipophilic part of the surfactant is located on the silane coupling agent side and the hydrophilic part is located on the outside.

  (Introduction step) Next, the introduction step will be described. In the introduction step, the reactive functional group of the protected silane coupling agent protected in the protection step is reacted with the polymer substrate (more specifically, the functional group possessed on the polymer substrate surface).

  More specifically, the protective silane coupling agent is added to the aqueous solution containing the polymer base material and the initiator in the protection step and reacted. In this case, specific examples of the initiator include ammonium persulfate and potassium persulfate (potassium peroxodioic acid). The aqueous solvent means a solvent containing at least 50% by weight of water, more preferably 80% by weight or more, and still more preferably 95% by weight or more. The aqueous solvent may contain, for example, alcohol such as methanol or ethanol.

  In the introduction step, when the protective silane coupling agent is introduced into the aqueous solvent containing the polymer base material, stirring is performed so that the protective silane coupling agent is uniformly dispersed on the surface of the polymer base material. It is more preferable.

  When the protective silane coupling agent comes into contact with the surface of the polymer substrate in an aqueous solvent, the reactive functional group of the protective silane coupling agent is exposed to the surface of the polymer substrate. The functional group present on the substrate surface reacts.

  The lower limit of the amount (addition amount) of the protective silane coupling agent is preferably 10% by weight or more, more preferably 50% by weight or more with respect to the polymer substrate having a functional group on the surface. More preferred is 100% by weight or more. If the amount used is less than 10% by weight, it may not be possible to introduce an alkoxysilyl group sufficient to react with a sufficient reactive substrate. On the other hand, the upper limit of the amount used is more preferably 500% by weight or less, further preferably 400% by weight or less, and particularly preferably 300% by weight or less. If the amount used is more than 500% by weight, it is not economical.

  The reaction is more preferably performed in a nitrogen atmosphere. As a lower limit of reaction temperature, 40 degreeC or more is more preferable, 45 degreeC or more is further more preferable, and 50 degreeC or more is especially preferable. When the reaction temperature is lower than 40 ° C., the reaction does not occur sufficiently and the alkoxysilyl group may not be introduced into the polymer substrate. On the other hand, the upper limit of the reaction temperature is more preferably 80 ° C. or less, further preferably 75 ° C. or less, and particularly preferably 70 ° C. or less. If the reaction temperature is higher than 80 ° C, the polymer substrate may be deteriorated. In addition, what is necessary is just to set suitably as reaction time so that it may become a desired introduction | transduction rate (ratio in which an alkoxy silyl group is introduce | transduced into a polymer base material).

  Further, the lower limit of the introduction rate (% by weight) of the alkoxysilyl group with respect to the polymer substrate is more preferably 0.1% by weight or more, and further preferably 1% by weight or more. Here, the introduction rate is the ratio of the weight of the protective silane coupling agent introduced per unit weight of the polymer substrate. When the introduction ratio is 0.1% by weight or more, sufficient strength can be exhibited when a composite is produced by reacting the polymer substrate with a reactive substrate. On the other hand, the upper limit of the introduction rate is not particularly limited, but if the introduction rate is higher than 100% by weight, it may not be economical.

  Also, for example, when the polymer substrate surface does not have a functional group, for example, the reactive functional group of the protective silane coupling agent is added to the polymer substrate subjected to corona treatment, plasma treatment, and UV treatment. It may be introduced directly. Also, for example, the reactive functional group of the protective silane coupling agent is introduced by generating a radical by extracting a proton (hydrogen atom) from the polymer substrate using a surfactant and a peroxide-based initiator. You can also.

  Here, the introduction process will be described in more detail. In the introduction step, the functional group present on the surface of the substrate is reacted with the reactive functional group of the protective silane coupling agent.

  That is, by reacting the functional group with the reactive functional group, a chemical bond is formed that binds the reactive functional group of the protective silane coupling agent to the functional group of the polymer substrate. .

  In this embodiment, the chemical bond formed by the reactive functional group of the protective silane coupling agent and the functional group of the polymer substrate has sufficient bond strength between the protective silane coupling agent and the polymer substrate. Although it will not specifically limit if it is obtained in (1), The chemical bond shown below can be mentioned as an example.

  These chemical bonds are obtained by reaction between reactive functional groups.

  Below, the case where the amide group shown by Chemical formula (2) is formed among the said exemplary chemical bonds is demonstrated concretely. The amide bond is a reaction between an amino group and a carboxyl group, an azidocarbonyl group, a chlorocarbonyl group, an N-hydroxysuccinimide carboxylic acid ester or an acid anhydride; a carboxyl group and an N-acetylamino group or an N-trimethylsilylamino group. The reaction of an isocyanate group with a carboxyl group; and the like. Appropriate reaction conditions vary depending on each combination, and the reaction conditions are not particularly limited as long as the reaction proceeds.

  For example, in the case of a combination of an amino group and a carboxyl group, first, a protective silane coupling agent and a surfactant obtained by the protection step are dispersed in an aqueous solvent containing a base material and an initiator that are dispersed. It reacts by throwing in. More specifically, after the protective silane coupling agent is dispersed on the surface of the polymer substrate, the reaction is performed under predetermined reaction conditions.

  At this time, the lower limit of the amount of the protective silane coupling agent used is more preferably 0.001 part by weight or more and further 0.01 part by weight or more with respect to 1 part by weight of the polymer substrate having a functional group. preferable. On the other hand, the upper limit of the amount of the protective silane coupling agent used is more preferably 100 parts by weight or less, and still more preferably 50 parts by weight or less, relative to 1 part by weight of the polymer base material having a functional group. If the lower limit is less than 0.001 part by weight, the protective silane coupling agent may not uniformly contact the surface of the polymer substrate, and the alkoxysilyl group may not be uniformly introduced. On the other hand, when the upper limit is more than 100 parts by weight, it is not economical.

  The solvent in which the protective silane coupling agent is dispersed is the above aqueous solvent. The reaction temperature may be about 50 ° C.

  Further, the ester bond represented by the chemical formula (3) is obtained by a reaction of a carboxyl group with a hydroxyl group, a diazocarbonyl group and / or a diazoalkyl group. Appropriate reaction conditions vary depending on each combination and are not particularly limited. Specifically, for example, a method of reacting a carboxyl group, which is a reactive functional group, with a hydroxyl group can be mentioned.

  The urea bond represented by the chemical formula (4) can be obtained, for example, by reacting an amino group with an isocyanate group.

  The thiourea bond represented by the chemical formula (5) can be obtained by reacting an amino group with an isothiocyanate group.

  The β-ketothioether bond represented by the chemical formula (6) is obtained by reaction of a mercapto group and an α-haloacetyl group. Although it does not specifically limit as reaction conditions, For example, the method etc. with which a mercapto group and (alpha) -haloacetyl group are made to react on the conditions of room temperature and the weak alkali of pH 7-8 in an aqueous medium are mentioned.

  The Schiff base structure represented by the chemical formula (7) is obtained by reacting an amino group with a moiety that can function as an aldehyde or a ketone. Examples of reaction conditions include a method of reacting both at room temperature in an alkaline aqueous solvent. Further, after obtaining the above Schiff base structure, for example, by reducing the Schiff base structure using a known reducing agent such as sodium borohydride or sodium cyanoborohydride, the chemical formula (8) is obtained. Secondary and tertiary amine structures can be obtained.

  The sulfamide bond represented by the chemical formula (9) is obtained by reacting an amino group with a sulfonyl chloride group or a sulfone group. Appropriate reaction conditions vary depending on the combination and are not particularly limited. Specifically, for example, in the case of a combination of an amino group and a sulfonyl group, an alkali having a pH of 9 to 10 is used in an aqueous solvent. There is a method of reacting under the following conditions.

  The hydroxy-secondary amine structure represented by the chemical formula (10) is obtained by a reaction between an amino group and an epoxy group. There are no particular limitations on the reaction conditions, but examples include a method of reacting in an aqueous solvent at room temperature and at a pH of 8 to 10.

  The carbamate bond represented by the chemical formula (11) can be obtained by reaction of a hydroxyl group with an isocyanate group or a carbonic acid diester.

The arylamine structure represented by the chemical formula (12) is obtained by reacting an amino group with a halogenated aryl group or a sulfonated aryl group. Appropriate reaction conditions vary depending on the combination and are not particularly limited. Specifically, for example, in the case of an amino group and an aryl halide group, an amino acid is used in an aqueous solvent under an alkaline condition. For example, a method of reacting a group with a halogenated aryl group. In the chemical formula (12), Ar ¹ represents an aryl group.

The aryl thioether bond represented by the chemical formula (13) is obtained by reacting a mercapto group with a halogenated aryl group or a sulfonated aryl group. Appropriate reaction conditions vary depending on the combination and are not particularly limited. Specifically, for example, in the case of a mercapto group and an aryl halide group, in an aqueous solvent containing methanol, 0 ° C. And a method of reacting a mercapto group and a halogenated aryl group using piperidine as a catalyst. Ar ² in the chemical formula (13) represents an aryl group.

  The sulfide bond represented by the chemical formula (14) is obtained by an exchange reaction between a mercapto group and a sulfide bond. Appropriate reaction conditions are not particularly limited, and examples thereof include a method of reacting a mercapto group and a sulfide bond at room temperature in an aqueous solvent having a pH of 7 to 8.

  The thioether bond represented by the chemical formula (15) can be obtained by reaction of a mercapto group with an acryloyl group or maleic imide.

  The β-aminothioether bond represented by the chemical formula (16) can be obtained by reaction of a mercapto group with aziridine or imine. Appropriate reaction conditions vary depending on the combination and are not particularly limited. Specifically, for example, in the case of a mercapto group and an aziridine group, the reaction is carried out in an aqueous solvent under weak alkaline conditions. There are methods.

  The vinyl bond represented by the chemical formula (17) is obtained by a vinyl polymerization reaction or the like.

  These chemical bonds are obtained by a reaction between the reactive functional group of the protective silane coupling agent and the functional group on the surface of the polymer substrate. Therefore, one of the combinations exemplified above may be a reactive functional group and the other may be a functional group. Specifically, for example, when an amide bond as shown in chemical formula (2) is obtained by a reaction between an amino group and a carboxyl group, the amino group may be the above functional group, or a reactive functional group. It may be. Similarly, the carboxyl group may be a reactive functional group or a functional group. However, regarding the functional group of the polymer base material, it is necessary to select a functional group that does not deactivate in an aqueous solvent.

  Thus, by performing the protection step and the introduction step, an alkoxysilyl group can be introduced into the polymer substrate even in an aqueous solvent.

  In the above example, the reaction is performed using the initiator. However, for example, the reaction can be performed even when the initiator is not used. Specifically, after adsorbing the protective silane coupling agent on the surface of the polymer base material, both (the reactive functional group and the functional group possessed by the polymer base material) can be reacted by applying heat. it can.

(Introductory)
By performing the introduction step and the introduction step, an introduction product in which an alkoxysilyl group is introduced onto the surface of the base material (polymer base material) can be obtained in an aqueous solvent. Accordingly, since the alkoxysilyl group is introduced on the surface of the substrate, the composite can be easily obtained by reacting the alkoxysilyl group with another substrate (reactive substrate). Moreover, since an alkoxysilyl group can be introduced even when an aqueous solvent is used, the cost for introducing an alkoxysilyl group can be reduced compared to the case of introducing it in an organic solvent. . When introducing an alkoxyl group into a polymer substrate by the above introduction method, it can be reacted in an aqueous solution, so that the safety of a polymer substrate into which an alkoxysilyl group has been introduced is improved with respect to the living body. Can do. Moreover, by using this introduction method, even when a silane coupling agent is used, an alkoxysilyl group can be introduced into the substrate without changing the properties of the substrate.

(Production method of composite)
Using the introduction method according to the present embodiment, the alkoxysilyl group of the base material into which the alkoxysilyl group is introduced on the surface of the base material, and the reactive base material that can react with the alkoxysilyl group (more specifically, the reactivity) By reacting with a reactive active group on the surface of the substrate, a complex in which the two substrates are chemically bonded can be produced. More specifically, the composite according to the present embodiment can be produced by performing the protection step, the introduction step, and the reaction step.

(Reaction process)
In the reaction step, the alkoxysilyl group introduced into the base material (polymer base material) and the reactive base material (more specifically, the reactive active group present on the surface of the reactive base material) by the introduction step described above React. Specifically, by immersing the substrate into which the alkoxysilyl group is introduced (hereinafter referred to as an introduced product) in a dispersion in which the reactive substrate is dispersed, the reactive substrate is formed on the surface of the introduced product. To adsorb. Then, the reactive active group of the reactive substrate adsorbed on the surface is reacted with the alkoxysilyl. In the following description, an example in which an alkoxysilyl group-introduced silk fibroin is used as the introduction and the reactive base material is a hydroxyapatite sintered body will be described. The alkoxysilyl group introduced into silk fibroin is protected with a surfactant. The hydroxyapatite sintered body is obtained by sintering amorphous hydroxyapatite.

  Specific examples of the dispersion medium for dispersing the hydroxyapatite sintered body include, for example, hydrocarbon solvents such as toluene and hexane; alcohols; ether solvents such as tetrahydrofuran and diethyl ether; ketones such as acetone and methyl ethyl ketone. Organic solvents such as system solvents; Of the solvents exemplified above, alcohols are preferably used in that the hydroxyapatite sintered body is well dispersed and the surfactant protecting the alkoxysilyl group is eliminated. As these dispersion media, only one type may be used, or a plurality of dispersion media may be used in combination. For example, when using a hydrocarbon solvent such as hexane or toluene, in order to disperse the hydroxyapatite sintered body satisfactorily, for example, (1) Stir vigorously with a stirrer such as a stirrer, (2) A method of dispersing using an ultrasonic device, (3) using the stirring device and the ultrasonic device in combination, or the like may be used.

  In the preparation of the dispersion liquid, the lower limit value of the added amount of the hydroxyapatite sintered body is more preferably 0.01% by weight or more, further preferably 0.02% by weight or more with respect to the dispersion medium. 05% by weight or more is particularly preferable. When the added amount of the hydroxyapatite sintered body is less than 0.01% by weight, the hydroxyapatite sintered body may not be uniformly adsorbed on the surface of the introduced product, and a uniform coated surface may not be formed. On the other hand, the upper limit of the added amount of the hydroxyapatite sintered body is more preferably 5.0% by weight or less, further preferably 4.0% by weight or less, and more preferably 3.0% by weight or less with respect to the dispersion medium. Is particularly preferred. When the amount added is more than 5.0% by weight, the amount of the hydroxyapatite sintered body remaining in the dispersion becomes significantly larger than the amount of the hydroxyapatite sintered body adsorbed on the surface of the introduction. Not economical.

  The lower limit of the reaction temperature at which the hydroxyl group of the hydroxyapatite sintered body adsorbed on the surface of the introduced product reacts with the alkoxysilyl group introduced into the introduced product is more preferably 25 ° C or higher, and more preferably 50 ° C or higher. More preferred is 80 ° C. or higher. When the reaction temperature is lower than 25 ° C., the hydroxyapatite sintered body and the alkoxysilyl group may not react. On the other hand, the upper limit of the reaction temperature is more preferably 200 ° C. or less, further preferably 175 ° C. or less, and particularly preferably 150 ° C. or less. When the reaction temperature is higher than 200 ° C., the introduced product may decompose.

  In addition, it is more preferable to wash the introduction with the same solvent as the dispersion medium after the introduction is immersed in the dispersion and before the reaction. Since the hydroxyapatite sintered body is laminated on the surface of the introduced material after being immersed in the dispersion, and the reaction is performed without washing, the hydroxyapatite sintered body is laminated, so that the physical properties of the introduced material are impaired. There is a case to make it.

  Moreover, you may make it react on vacuum conditions as needed. By reacting a hydroxyapatite sintered body with an alkoxysilyl group under vacuum conditions, a hydroxyapatite composite can be produced more quickly. In addition, when making it react on vacuum conditions, as a pressure which performs reaction, the inside of the range of 0.01 mmHg (1.33 kPa)-10 mmHg (13.3 kPa) is preferable. By setting the pressure within the above range, methanol (ethanol) generated when the hydroxyl group of the hydroxyapatite sintered body reacts with the alkoxysilyl group can be removed.

  In addition, what is necessary is just to change suitably the reaction conditions of the said reaction process, the kind of solvent, etc. according to the kind of polymeric base material, and the reactive base which exists in the reactive base material or the reactive base surface.

(Complex)
The composite according to this embodiment can be obtained by the above-described method for manufacturing a composite. That is, in the composite according to the present embodiment, the base material and the reactive base material are chemically bonded via the silane coupling agent.

  And when the base material and the reactive base material which comprise the said composite_body | complex are medical materials, the obtained composite body can be used suitably as a medical material.

In addition, when the reactive base material has a hydroxyl group and the alkoxysilyl group introduced into the base material is —Si≡ (OR) ₃ , the reactive base material is interposed between the reactive base material and the base material. In this case, a bond represented by the chemical formula (18) is present.

(However, X represents a substrate, and Y represents a reactive substrate.)
In the above case, the three hydroxyl groups present on the substrate surface are reacted with one alkoxysilyl group (—Si≡ (OR) ₃ ) introduced into the substrate. Therefore, for example, even if the base material has a small number of introduced alkoxysilyl groups, a large number of base materials can be bonded and more firmly bonded. In addition, the silicon atom (Si) of the chemical formula (18) is a part of the alkoxysilyl group introduced into the base material. Moreover, the oxygen atom (O) of the chemical formula (18) is a part of the alkoxysilyl group of the base material or a part of the hydroxyl group of the reactive base material. Further, X and Si in the chemical formula (18) may be bonded with a polymer chain, may be bonded with a low molecular chain, or may be directly bonded.

  Further, in the composite produced by the above production method, the base material and the reactive base material are chemically and strongly bonded. Therefore, by selecting the type of the base material and the reactive base material, for example, Percutaneous medical devices such as percutaneous catheters and percutaneous terminals; artificial organs such as artificial blood vessels and artificial organs; medical materials such as catheters for urination, artificial bones and stents; separation of substances such as liquid column chromatography and gas chromatography Separation support for building materials; Building materials such as wall materials and environmental materials with the function of decomposing substances affecting the human body such as formaldehyde; Keeping things used in hospitals such as curtains and sheets clean Functional hygiene materials and bedding used in general households; textile materials such as clothes; tableware and glass materials such as glasses and cups; materials for electronic components such as semiconductors ; It can be suitably used in, and the like; metal plating materials for modifying the metal surface; coating material used for the outer wall, such as a house or a ship.

  As described above, the introduction method according to the present embodiment has a configuration including the protection step of protecting the alkoxysilyl group-containing compound with the surfactant and the introduction step of introducing the alkoxysilyl group into the substrate. By protecting the alkoxysilyl group-containing compound containing an alkoxysilyl group with a surfactant, the alkoxysilyl group can be introduced into the substrate even in an aqueous solvent. Moreover, since an alkoxysilyl group can be introduced in an aqueous solvent, the treatment of the solvent is simplified and the cost for the solvent can be reduced.

  In the introduction method according to the present embodiment, it is more preferable to perform a functional group introduction step of introducing a functional group capable of reacting with the reactive functional group to the substrate. Thereby, since the said reactive group should just be introduce | transduced into a base material, the freedom degree of selection of a base material becomes high. That is, even when the substrate itself does not have the reactive group, an alkoxysilyl group can be introduced.

  The method for producing a composite according to the present embodiment includes a protection step of protecting an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant, and a protected alkoxy protected by the protection step. An introduction step of introducing an alkoxysilyl group into the substrate by reacting the reactive functional group of the silyl group-containing compound with the substrate capable of reacting with the reactive functional group in an aqueous solvent, and introduction into the substrate And a reaction step in which a reactive substrate capable of reacting with the alkoxysilyl group is reacted. According to said structure, the base material in which the alkoxy silyl group was introduce | transduced and the reactive base material can be chemically bonded in an aqueous solvent. Thereby, the safety | security at the time of using for the biomaterial of the composite_body | complex finally obtained can be made still higher, for example. In addition, the composite can be produced while maintaining the properties of the substrate itself.

  Here, a functional group introduction step for introducing a functional group onto the substrate surface will be described. Specifically, a method for introducing a vinyl group into a base material using silk fibroin as the base material (polymer base material) will be described.

  In order to introduce a vinyl group which is a functional group into a polymer substrate, for example, the polymer substrate has a functional group capable of reacting with a reactive functional group and a reactive group capable of reacting with the polymer substrate. The functional group-containing compound may be reacted in a mixed solution of a catalyst, a polymerization inhibitor and a solvent. About the said reactive group, it selects suitably by the kind of polymer base material.

  Specific examples of the functional group-containing compound include 2-methacryloyloxyethyl isocyanate and hexamethylene diisocyanate. The solvent is preferably a polar solvent, and for example, dehydrated dimethyl sulfoxide, dehydrated dimethylformamide and the like are preferably used. The polymerization inhibitor is added so that the functional groups introduced into the polymer substrate and the functional group-containing compounds do not polymerize. Examples of the polymerization inhibitor include hydroquinone. Examples of the catalyst include dibutyltin (IV) dilaurate.

  The lower limit of the amount of the functional group-containing compound added is more preferably 10% by weight or more, further preferably 50% by weight or more, and particularly preferably 100% by weight or more based on the polymer substrate. If the amount added is less than 10% by weight, a sufficient amount of functional groups may not be introduced into the polymer substrate. On the other hand, the upper limit of the addition amount is more preferably 500% by weight or less, still more preferably 400% by weight or less, and particularly preferably 300% by weight or less with respect to the polymer substrate. When the added amount is more than 500% by weight, it is not economical.

  And as a lower limit of reaction temperature, 30 degreeC or more is more preferable, 40 degreeC or more is further more preferable, and 45 degreeC or more is especially preferable. If the said reaction temperature is lower than 30 degreeC, reaction will not fully occur and a functional group may not be introduce | transduced into a polymer base material. On the other hand, as an upper limit of reaction temperature, 100 degrees C or less is more preferable, 80 degrees C or less is further more preferable, and 60 degrees C or less is especially preferable. If the reaction temperature is higher than 100 ° C, the functional groups introduced into the polymer substrate may react with each other. In addition, the polymer base material may be deteriorated. In addition, what is necessary is just to set reaction time suitably by reaction temperature etc. By reacting under the above conditions, functional groups can be easily introduced into the polymer substrate.

  The lower limit of the functional group introduction rate (% by weight) with respect to the polymer substrate is more preferably 0.1% by weight or more, still more preferably 1.0% by weight or more, and particularly preferably 2.0% by weight or more. If the introduction rate is less than 0.1% by weight, the number of alkoxysilyl groups introduced into the polymer substrate may be reduced, making it impossible to produce a composite. On the other hand, the upper limit of the introduction rate is more preferably 30% by weight or less, further preferably 25% by weight or less, and particularly preferably 20% by weight or less. When the introduction ratio is more than 30% by weight, the number of functional groups introduced into the polymer base material may increase, and the functional groups may react with each other.

  Moreover, about the reactive active group introduction | transduction process which introduce | transduces a reactive active group into the reactive base material surface, it has a reactive active group which can react with an alkoxy silyl group, and an active group which can react with a reactive base material This can be carried out by reacting the reactive group-containing compound with a reactive substrate.

  Further, for example, when the reactive functional group of the alkoxysilyl group-containing compound is an alkoxysilyl group, that is, when it has two or more alkoxysilyl groups per molecule, the substrate and the reactive substrate are inorganic materials. The composite which consists of can be manufactured.

  Moreover, when the reactive base material is, for example, an organic polymer having a hydroxyl group on the surface, a composite body in which the base material and the reactive base material are made of an organic material can be produced.

  Moreover, in the manufacturing method of a composite_body | complex, you may perform the desorption process which remove | eliminates the surfactant which is protecting the silane coupling agent before performing a reaction process. Specifically, for example, in order to desorb the surfactant, the substrate into which the alkoxysilyl group protected by the surfactant is introduced may be washed using a solvent such as alcohol or toluene. . Thereby, surfactant can be desorbed. The solvent for desorption may be any solvent as long as R in the Si-OR of the alkoxysilyl group does not replace H, for example.

  Further, the desorption step and the reaction step may be performed simultaneously. Specifically, if the solvent used in the desorption step and the solvent used in the reaction step are the same, the surfactant can be desorbed and the alkoxysilyl group can react with the reactive substrate. it can.

  In Example 1 below, a composite is manufactured using silk fibroin as a substrate and hydroxyapatite sintered particles as a reactive substrate. First, the manufacturing method of the said hydroxyapatite sintered compact is demonstrated.

(Method for producing hydroxyapatite sintered body)
Using dodecane as a continuous oil phase and pentaethylene glycol dodecyl ether having a cloud point of 31 ° C. as a nonionic surfactant, 40 ml of a continuous oil phase containing 0.5 g of the nonionic surfactant was prepared. Next, 10 ml of Ca (OH) ₂ dispersed aqueous solution (2.5 mol%) was added to the adjusted continuous oil phase. Then, after stirring thoroughly resulting dispersion with the aqueous / oil (W / O) was added to 1.5 mol% of _KH 2 PO ₃ solution 10ml to emulsions, the reaction temperature 50 ° C., The reaction was allowed to stir for 24 hours. Hydroxyapatite was obtained by separating the obtained reaction product by centrifugation. And the particle | grains of the hydroxyapatite sintered compact were obtained by heating the said hydroxyapatite on 800 degreeC conditions for 1 hour. This hydroxyapatite sintered body was a single crystal and had a major axis of 100 to 250 nm.

(Production method of composite)
First, 73 mg of pentaethylene glycol dodecyl ether which is a nonionic surfactant and 323 mg of methacryloxypropyltrimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., product number KBM-503; hereinafter referred to as KBM) are mixed to prepare a reagent. did. In a test tube, a fibrous silk fibroin, which is a polymer base material that was vacuum-dried for a whole day and night (manufactured by Fujimura Yarn Co., Ltd., product name: Hanebi, hereinafter referred to as “SF fiber”) 50 mg 6 ml of distilled water and ammonium persulfate 41 mg was added, and the reagent was added and stirred therein. Next, the inside of the test tube was sufficiently degassed and filled with nitrogen gas, and then sealed. And by making it react at 50 degreeC for the predetermined time, SF fiber (henceforth KBM-SF) which graft-polymerized the polymer chain which has an alkoxy silyl group at the terminal was obtained. Table 3 shows the introduction rate (%) of the alkoxysilyl group during the reaction time. In addition, the said introduction rate was calculated | required by the following Formula (1) by making the weight of untreated SF fiber into eg and the weight of KBM-SF as fg.

    Introduction rate (%) = ((f−e) / e) × 100 (1)

  Moreover, the FT-IR analysis result of KBM-SF obtained as described above is as shown in FIG. In the figure, untreated SF is a spectrum showing the result of FT-IR of the polymer substrate itself, and the lower spectrum shows the FT-IR spectrum of KBM-SF.

  And the hydroxyapatite sintered compact particle | grains manufactured as mentioned above were disperse | distributed in the ratio of 5 mg / ml in the mixed solvent whose toluene: methanol volume ratio is 8.8: 1, and left still for 1 hour. Then, the KBM-SF having a diameter of 1.8 cm was immersed therein. And after taking out said KBM-SF and fully wash | cleaning with the said mixed solvent, 120 degreeC and the coupling reaction were performed for 2 hours. After the reaction, the obtained reaction product is immersed in distilled water and treated with a probe-type ultrasonic generator (same as above) for 3 minutes under the conditions of an output of 20 kHz and 35 W, and unreacted hydroxyapatite sintered particles. The hydroxyapatite composite according to the present invention was obtained by removing. The obtained hydroxyapatite composite was observed with a scanning electron microscope. The result is shown in FIG.

  From the above results, it can be seen that the hydroxyapatite sintered particles are bonded to the surface of the SF fiber.

  The composite according to the present embodiment includes, for example, percutaneous medical devices such as percutaneous catheters and percutaneous terminals; artificial materials such as artificial blood vessels and artificial organs, catheters for urination, artificial bones, and stents; Separation carrier for separating substances such as liquid column chromatography and gas chromatography; environmental materials with functions to decompose building materials such as wall materials and substances that affect the human body such as formaldehyde; curtains Sanitary materials with the function to keep things used in hospitals such as sheets clean and bedding used in general households; textile materials such as clothes; tableware materials and glass materials such as glasses and cups; semiconductors, etc. It is suitable for applications such as materials for electronic parts; coating materials used for outer walls of houses and ships; metal plating materials for modifying metal surfaces;

4 is a spectrum showing the FT-IR analysis result of KBM-SF of Example 1. 2 is a drawing showing a microscopic image of the surface of the composite of Example 1. FIG.

Claims (13)

A protective step of protecting an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant;
By reacting the reactive functional group of the protected alkoxysilyl group-containing compound protected by the above-mentioned protective step and the base material capable of reacting with the reactive functional group in an aqueous solvent, the alkoxysilyl group is formed on the base material. An alkoxysilyl group introduction method comprising an introduction step of introducing.   The method for introducing an alkoxysilyl group according to claim 1, wherein the substrate has a functional group capable of reacting with a reactive functional group on the surface of the substrate.   2. The alkoxysilyl group introduction method according to claim 1, further comprising a functional group introduction step of introducing a functional group capable of reacting with the reactive functional group into the substrate before the introduction step.   An introduced product comprising an alkoxysilyl group introduced to the surface of a substrate by the alkoxysilyl group introducing method according to any one of claims 1 to 3.   The introduction according to claim 4, wherein the substrate is silk fibroin. A protection step of protecting an alkoxysilyl group-containing compound containing an alkoxysilyl group and a reactive functional group with a surfactant;
An alkoxysilyl group is introduced into the base material by reacting the reactive functional group of the protected alkoxysilyl group-containing compound protected by the above-described protection step with the base material capable of reacting with the reactive functional group in an aqueous solvent. An introduction process to
The manufacturing method of the composite_body | complex characterized by including the reaction process with which the alkoxysilyl group introduce | transduced into the base material and the reactive base material which can react with the said alkoxysilyl group are made to react.   The said base material has a functional group which can react with a reactive functional group, The manufacturing method of the composite_body | complex of Claim 6 characterized by the above-mentioned.   The method for producing a composite according to claim 6, further comprising a functional group introducing step of introducing a functional group capable of reacting with the reactive functional group into the substrate before the introducing step.   The method for producing a composite according to any one of claims 6 to 8, wherein the surface of the reactive base has a reactive active group capable of reacting with the alkoxysilyl group. .   The reactive active group introducing step of introducing a reactive active group capable of reacting with the alkoxysilyl group into the reactive base material before the reacting step is included. A method for producing the composite according to 1.   The production of the complex according to any one of claims 6 to 10, further comprising a desorption step of desorbing the surfactant protecting the alkoxysilyl group-containing compound after the introduction step. Method.   The composite_body | complex manufactured by the manufacturing method of the composite_body | complex of any one of Claims 6-11.   The composite according to claim 12, wherein the substrate is silk fibroin, and the reactive substrate is a hydroxyapatite sintered body.