JP2012095969A - Compound base material and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound base material that maintains a high antibacterial property for a long period of time, and a method of manufacturing the same.SOLUTION: The compound base material comprises a base material, fine particles of substitution type calcium phosphate in which a part of calcium ions in calcium phosphate is substituted by an antibacterial metal and hydrolyzate and/or condensate of a coupling agent which couple them.

Description

  The present invention relates to a composite substrate and a method for producing the same.

  Inorganic antibacterial agents have high heat resistance and safety, and can be expected to have a semi-permanent effect. Therefore, the use of synthetic organic antibacterial agents has become increasingly popular in plastics, fibers, ceramics, etc. Shows market expansion.

  In recent years, as the hygiene consciousness of society as a whole has increased due to mass food poisoning, hospital infections, etc., a wide variety of antibacterial products using these inorganic antibacterial agents have been put into practical use. There is a growing demand for products with antibacterial properties. From an industrial point of view, the demand for filters, films, and the like containing these antibacterial substances is increasing.

  Patent Document 1 discloses an antibacterial resin composition containing zeolite and a resin carrying antibacterial metal ions such as silver ions. Patent Documents 2 to 6 disclose phosphate particles or hydroxyapatite particles carrying antibacterial metal ions such as silver, zinc and copper ions, or resin compositions containing such particles. . Since these antibacterial substances use zeolite or hydroxyapatite as a carrier, they have both excellent adsorptivity and antibacterial properties. However, when these particles are kneaded into a polymer (base material, fiber), the exposed surface to the outside becomes a very small amount, so that the excellent antibacterial properties of the particles are not utilized. Further, the particle diameter of these particles is several μm to several tens μm, and it is a big problem that the physical properties of the substrate are greatly deteriorated and the particles are peeled off.

  On the other hand, in Patent Document 7, nuclei of hydroxyapatite particles are formed on the surface of the fiber, and then hydroxyapatite is grown to form a film made of hydroxyapatite on the surface of the fiber. Next, a method for producing antibacterial fibers is described in which a fiber with a hydroxyapatite film is immersed in an aqueous solution in which an antibacterial metal salt is dissolved. In the antibacterial fiber produced by this method, a film made of hydroxyapatite is formed on the surface of the fiber, and the antibacterial metal, its ion or salt is supported on this film. For this reason, most of these metals, ions or salts thereof can have a function as an antibacterial agent.

Japanese Patent Publication No. 63-54013 Japanese Patent Laid-Open No. 2-96508 JP-A-2-180270 JP-A-3-43457 JP-A-3-38504 JP-A-3-83905 Japanese Patent No. 3777387

  However, in the method for producing an antibacterial fiber described in Patent Document 7, since the hydroxyapatite is physically or electrostatically fixed to the fiber (base material), the adhesive strength between the hydroxyapatite and the base material is high. It is weak and the long-term durability of the antibacterial effect in actual use is insufficient. In order to increase the adhesive strength, it may be possible to join the hydroxyapatite and the base material with an adhesive. In this case, however, the adhesive covers the surface of the hydroxyapatite, reducing the antibacterial properties and adsorption capacity. There is a fear. Moreover, when such a fiber is used in water, there exists a possibility that an adhesive agent may elute.

  Then, this invention solves the said problem, and aims at providing the composite base material which can maintain high antimicrobial property over a long period of time, and this manufacturing method.

  The composite base material of the present invention comprises a base material, a substituted calcium phosphate fine particle in which a part of calcium in calcium phosphate is replaced with an antibacterial metal, a hydrolyzate of a coupling agent and / or its A condensate.

  By adopting such a configuration, the composite base material of the present invention can exhibit high antibacterial properties because the fine particles of substituted calcium phosphate substituted with an antibacterial metal are uniformly distributed on the base material. In addition, since the base material and the substituted calcium phosphate fine particles are joined by the hydrolyzate of the coupling agent and / or its condensate, the adhesion between them is excellent, and the antibacterial property is maintained for a long time. it can.

  Moreover, in the antibacterial fiber by the manufacturing method described in Patent Document 7, a hydroxyapatite film having a thickness of 10 to 25 μm is formed on the fiber. Such a film is obtained by bending a base material (woven fabric). At this time, peeling or cracking of the film is likely to occur. On the other hand, the composite base material described above has several tens to several hundreds of layers of the hydrolyzate of the coupling agent and / or the condensate thereof in addition to the point that the calcium phosphate fine particles are scattered on the base material. Since it exists as a thin film of about nm, the flexibility and elasticity inherent in the base material are not greatly impaired. For this reason, it can be widely used in general antibacterial processed products such as filters, masks, building materials, table cloths, curtains and clothes.

  The hydrolyzate of the coupling agent is preferably an alkoxysilane hydrolyzate. Since the coupling agent made of alkoxysilane strongly bonds the base material and the substituted calcium phosphate fine particles by hydrolysis and condensation, the adhesive strength between the two can be reliably increased.

  The calcium phosphate fine particles in the present invention are one or more metals in which 0.01 to 30% by mass of calcium ions in the calcium phosphate is selected from the group consisting of copper, silver, zinc, iron, lead, nickel, cobalt, palladium and platinum. It is preferably substituted with ions. In this case, since some of the calcium ions in the calcium phosphate are replaced with metal ions having antibacterial properties, they act effectively as an antibacterial material.

The hydrolyzate of alkoxysilane is preferably a product obtained by hydrolyzing the alkoxysilane represented by the general formula (1) or (2) in an alcohol solvent.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]

  The total amount of the fine particles and the hydrolyzate of the coupling agent and / or the condensate thereof is preferably 0.1 to 10% by mass with respect to the substrate. When the total amount is within the above range, the influence on the flexibility and elasticity of the substrate can be suppressed.

  The calcium phosphate is preferably hydroxyapatite. In this case, viruses and fungi can be collected by the adsorptive property of hydroxyapatite, so that the antibacterial property of the composite substrate can be further enhanced.

  Examples of the substrate include natural fibers, synthetic fibers, and glass fibers, or polymer films or glass substrates.

  A method for producing a composite substrate is a fine particle arranging step in which fine particles of substituted calcium phosphate in which a part of calcium in calcium phosphate is replaced with an antibacterial metal are arranged on a coupling agent coated surface of a substrate coated with a coupling agent. including.

  In the method for producing an antibacterial fiber described in Patent Document 7, it takes 8 days to form a hydroxyapatite nucleus on the surface of the fiber (base material), and further precipitates and grows hydroxyapatite on the surface of the fiber. It takes 5 to 10 days to form a film. On the other hand, in the above manufacturing method, unlike the manufacturing method described in Patent Document 7, a process that takes a long time is unnecessary, and the manufacturing period of the composite substrate can be shortened.

  The fine particle arranging step is a step of immersing the base material coated with the coupling agent in an aqueous solution having a pH of 7 or more containing calcium ions, phosphate ions and antibacterial metal ions.

  The fine particle arranging step includes a step of immersing the base material coated with the coupling agent in an aqueous solution containing calcium ions and phosphate ions having a pH of 7 or more to arrange the calcium phosphate fine particles on the surface, and a group on which the calcium phosphate fine particles are arranged. The material is immersed in an aqueous solution of at least one salt selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, acetate, and sulfate, and a part of calcium ions in the calcium phosphate fine particles is made into metal Substituting with ions.

  The coupling agent is preferably an alkoxysilane.

  The manufacturing method of the composite substrate further includes a heating step of heating the substrate on which the fine particles are arranged.

In the fine particle arranging step and / or the heating step, it is preferable that a hydrolyzate of the coupling agent represented by the general formula (1) or (2) is formed.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]

  The heating step is preferably a step of heating the substrate on which the calcium phosphate fine particles are arranged at 20 to 200 ° C.

  The present invention also provides an antibacterial member, an antibacterial filter, a mask, wallpaper, a curtain, or a table cloth made of the composite base material described above.

  ADVANTAGE OF THE INVENTION According to this invention, the composite base material which can maintain high antimicrobial property over a long term, and this manufacturing method can be provided.

It is a schematic diagram of the structure of the composite base material which concerns on this embodiment. 2 is an SEM image (magnification 2000 times) of the composite substrate obtained in Example 1. FIG.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The composite base material is composed of a base material, a substituted calcium phosphate fine particle in which a part of calcium ions in the calcium phosphate is substituted with an antibacterial metal ion, a hydrolyzate of a coupling agent and / or its A condensate. FIG. 1 shows a substitution in which the base material is an organic base material, the coupling agent is a silane coupling agent, and the substituted calcium phosphate fine particles are replaced with part of calcium in hydroxyapatite with Ag, which is an antibacterial metal. The schematic diagram of a structure of the composite base material in the case of the type | mold calcium-phosphate fine particle is shown. As shown in FIG. 1, in the composite base material, the base material and the substituted calcium phosphate fine particles are joined by a hydrolyzate of the coupling agent and / or a condensate thereof. For this reason, the adhesive force between both is excellent and antimicrobial property can be maintained over a long period of time. Hereinafter, each component is described in order.

(Base material)
Base materials are woven fabrics, non-woven fabrics, knitted fabrics, felts (those made of wool and other animal hairs that have been shrunk by applying steam, heat, or pressure to form a cloth), films, sheets, plates, or curved surfaces But no problem. If a part or the whole of the substrate shape is cylindrical, mesh-like, thread-like, tube-like, foamed or the like, if it can be immersed and the solution can enter, the hydrolyzate of alkoxysilane described below and Since the condensate is / is formed on the surface, there is no problem, and it may be appropriately selected according to the use. Even if the substrate surface has irregularities on the nanometer scale or submicron scale, there is no problem because the hydrolyzate of alkoxysilane forms a thin film following the structure.

(Woven fabric)
The woven fabric or the nonwoven fabric is not particularly limited as long as it is composed of fibers having an average fiber diameter of 1 to 100 μm, preferably 1 to 60 μm, and any woven fabric composed of natural fibers, synthetic fibers, and mixed fibers thereof. -Nonwoven fabric can be used. Further, the fiber may be any of various natural fibers and synthetic fibers. Specific examples of natural fibers include plant fibers such as cotton, hemp and bamboo. Examples of animal fibers include wool, silk tengu thread, mohair and cashmere. There is no problem even if fibers other than those listed here are used.

The thicknesses of the woven fabric and the non-woven fabric are not particularly limited and vary depending on the use, but are preferably about 0.001 to 10 mm, and more preferably about 0.01 to 5 mm. Further, the basis weight (weight per unit of woven fabric or knitted fabric) when using a woven fabric or a nonwoven fabric as a base material is not particularly limited, but is preferably ² to 100 g / mm ² , and preferably 10 to 70 g / mm. ² is more preferable.

(Synthetic fiber / woven fabric)
A polymer substrate can be used as the substrate. Polymer base materials include polyether, polyether ketone, polyamine, polyurea, polyimide, polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, polyethylene glycol, polyalkylene glycol, polyglycolic acid, polylactic acid, polyamide, polyurethane , Synthetic polymers such as polysulfone, polyester, polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile, polystyrene, polyvinyl alcohol, polyethylene terephthalate, polyvinyl chloride; polypeptides such as cellulose, amylose, amylopectin, collagen, hyaluronic acid, Mucopolysaccharides such as chondroitin and chondroitin sulfate, silicone resin (may be silicone rubber), acrylic resin, phenol resin Epoxy resin, natural polymer, and the like silk fibroin and the like. Among the polymer base materials exemplified above, polyurethane, silk fibroin, silicone resin, and the like can be suitably used because they have excellent long-term stability, strength, flexibility and other characteristics. In terms of material cost, polyethylene, polypropylene, polyethylene terephthalate, etc. are inexpensive and can be used preferably.

(Alkoxysilane)
The composite base material includes a base material, a substituted calcium phosphate fine particle in which a part of calcium ions in the calcium phosphate is substituted with an antibacterial metal, and a hydrolyzate of a coupling agent and / or a condensate thereof. And comprising. Here, the hydrolyzate of the coupling agent is preferably an alkoxysilane hydrolyzate. The hydrolyzate of alkoxysilane is preferably prepared by hydrolyzing the alkoxysilane represented by the general formula (1) or (2) in an alcohol solvent.
Si (OR) ₄ (1)
R'n-Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]

  The alkoxysilane may be hydrolyzed using an organic solvent, water, and an acid / alkali catalyst. The obtained product may be a mixture containing a condensate, an unreacted product and the like. Specific examples of alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane as tetrafunctional alkoxysilane, and methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyl as trifunctional alkoxysilane. Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidpropoxytrimethoxysilane, glycylpropylmethyldiethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, Mercaptopropyltrimethoxysilane and bifunctional alkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxy. Silane, and the like diphenyl diethoxy silane. These alkoxysilanes can be used alone or in combination of two or more. Alkoxysilane has a role of chemically bonding with an organic material. Therefore, since the bonding property with the base material depends on the functional group in the alkoxysilane, it is possible to further increase the binding property with the base material by using a reactive functional group. Specific examples of the functional group include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an amino group, a chloropropyl group, an acryloxy group, a sulfide group, an isocyanate group, a phenyl group, a benzyl group, and a mercapto group. By using alkoxysilanes having these functional groups, it is possible to adjust the adhesive force between the substrate and fine particles of substituted calcium phosphate described later.

  Condensation products of alkoxysilanes such as ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, methyl silicate 51, ethyl silicate 53A, ethyl silicate 53A, n-propyl silicate, n-butyl silicate, etc. manufactured by Colcoat Co., Ltd. A thing can also be used and it may use two or more types together. Since these alkoxysilane condensates (oligomers) have a high solid content and excellent reactivity, they can firmly fix the fine particles of hydrophilic substituted calcium phosphate and are relatively inexpensive.

(Alkoxysilane hydrolyzate / condensate)
The alkoxysilane hydrolyzate and / or its condensate that joins the substrate and substituted calcium phosphate fine particles are (1) unreacted alkoxysilane and (2) -SiOR in alkoxysilane is changed to -SiOH. (3) a polymer of alkoxysilane, and (4) a hydrolyzate of alkoxysilane in contact with calcium phosphate, and then the silanol group (—Si—OH) contained in the molecule becomes a hydroxyl group on the surface of calcium phosphate ( It may include those in a state where they are dehydrated and condensed with —OH) and changed to —Si—O— bonds.

  A known method can be used for hydrolysis of alkoxysilane (see JP-A-6-52796). To give a specific example, the temperature is from room temperature to 60 ° C. (preferably from room temperature to 30 ° C.) using water and an acid catalyst or a base catalyst that is about 0.01 to 10 times the number of moles of tetramethoxysilane. The hydrolysis reaction is carried out with stirring for 1 hour or longer (preferably 2 to 5 hours). In order to prepare a homogeneous thin film, it is appropriate to further dilute with a solvent to prepare a solution having a silane concentration of 30% by mass or less, more preferably 1 to 10% by mass.

  The catalyst used in the hydrolysis reaction may be either an acid catalyst or a base catalyst. Specifically, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, and aqueous ammonia as the base catalyst can be suitably used as the acid catalyst. Among these catalysts, phosphoric acid is preferably used when it is desired to reduce impurities in the substituted calcium phosphate, and ammonia water is preferably used when a dense film is formed.

  Dilution solvents include alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol and 2-butanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, and the like. Examples thereof include a mixed solvent. It is preferable to add these organic solvents to the hydrolyzed solution (hereinafter referred to as hydrolyzed solution) and further dilute it, and use it as a solid content concentration of 0.1% by mass or more and less than 5% by mass. For example, when an alcohol solvent is used, the storage stability of the hydrolyzate improves as the alcohol having a higher carbon number is used.

(Substituted calcium phosphate)
Substituted calcium phosphate is a compound obtained by substituting a part of calcium ions in calcium phosphate with antibacterial metal ions having antibacterial properties described later, and exhibits excellent antibacterial properties. Since the substituted calcium phosphate fine particles are firmly bonded to the base material by the hydrolyzate of alkoxysilane and / or the condensate thereof, it can be prevented from peeling from the base material. As a result, excellent antibacterial properties last for a long time. The adhesion amount of the fine particles is preferably 0.01 to 10% by mass with respect to the base material. If the adhesion amount is too large, peeling is likely to occur, and the flexibility and elasticity of the substrate are affected.

The total amount of the substituted calcium phosphate fine particles and the hydrolyzate and / or condensate of the coupling agent is preferably 0.1 to 10% by mass with respect to the substrate. When the total amount is within the above range, the influence on the flexibility and elasticity of the substrate can be suppressed. The total amount is more preferably 3.0 to 7.0% by mass.

  The fine particles of substituted calcium phosphate are more preferably in the form of particles. The specific particle size (average particle size) is preferably 0.001 μm to 5 μm from the viewpoint of further improving the adhesion to the substrate surface after ultrasonic irradiation and the antibacterial property, and 0.01 to 0. 5 μm is more preferable, and 0.03 to 0.3 μm is particularly preferable. The particle diameter of the fine particles bonded to the substrate can be measured by direct observation using a scanning electron microscope (SEM) or the like. The particle diameter in the present embodiment refers to the long axis (the longer one of the two orthogonal axes of the ellipse).

Specifically, as calcium phosphate, primary calcium phosphate {Ca (H ₂ PO ₄ ) ₂ .H ₂ O}, dicalcium phosphate (CaHPO ₄ ), dicalcium phosphate (anhydrous) {CaHPO ₄ .2H ₂ O}, Tricalcium phosphate {3Ca ₃ (PO ₄ ) ₂ · Ca (OH) ₂ }, tricalcium phosphate {Ca ₃ (PO ₄ ) ₂ }, α-type tricalcium phosphate {α-Ca ₃ (PO ₄ ) ₂ } Β-type tricalcium phosphate {β-Ca ₃ (PO ₄ ) ₂ }, hydroxyapatite {Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ }, tetracalcium phosphate {Ca ₄ (PO ₄ ) ₂ O}, Examples include calcium pyrophosphate (Ca ₂ P ₂ O ₇ ) and calcium pyrophosphate dihydrogen (CaH ₂ P ₂ O ₇ ). Of these, hydroxyapatite is preferred. Hydroxyapatite exhibits not only a role as a support but also excellent adsorption properties. Further, it is a material exhibiting biocompatibility, and is also preferable in terms of low environmental load. The OH in the structure ^- even superior reactivity with the alkoxysilane having a.

Hydroxyapatite is a kind of calcium phosphate and is represented by the chemical formula: Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ . As hydroxyapatite, a compound in which a part of the structure is replaced with another element can be used. The stoichiometric composition formula of hydroxyapatite is Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , but may be a non-stoichiometric composition such as Ca-deficient hydroxyapatite. That is, in the present embodiment, non-stoichiometric materials such as Ca-deficient hydroxyapatite and hydroxyapatite are considered. Specifically, hydroxyapatite is theoretically formed at a molar ratio of Ca / P = 1.66, but Ca / P may be 1.4 to 1.8.

Hydroxyapatite can replace some of the ions in the structure with other elements as long as the properties are not impaired. An apatite compound typified by hydroxyapatite is a composition represented by the following general formula (3), and there are various combinations of compounds by substituting M, ZO ₄ and X.
M ₁₀ (ZO ₄ ) ₆ X ₂ (3)

In the general formula (3), a metal ion capable of substituting calcium is placed at the position of the atom M that gives a cation (Ca ^{2+ in} the case of calcium ion). Specifically, sodium, magnesium, potassium, aluminum, Scandium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, strontium, yttrium, zirconium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, barium, lanthanum, cerium, praseodymium, neodymium, Examples include ions of samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, platinum, gold, mercury, thallium, lead, bismuth, etc. In addition, an oxide ion that can be substituted for PO ₄ ³⁻ enters the position of ZO ₄ , and CO ₃ ²⁻ , CrO ₄ ³⁻ , AsO ₄ ³⁻ , VO ₄ ³⁻ , UO ₄ ³⁻ , SO ₄ ^{2. −} , SiO ₄ ⁴⁻ , GeO ₄ ^{4− and the} like enter. At the position of X, a negative ion capable of substituting for OH ⁻ is entered, and halide ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), BO ²⁻ , CO ₃ ²⁻ , O ^{2− and the} like are entered. The ion substituted M, the ZO 4, _X may also be either one kind or two or more kinds.

Here, X is preferably OH ⁻ and F ⁻ . In the case of OH ⁻ , it is preferable in terms of excellent reactivity with alkoxysilane due to increased hydrophilicity, and in the case of F ^−, it is preferable in terms of excellent strength and that it can be stably present even in an acidic atmosphere. .

  Substituted calcium phosphate exhibits excellent antibacterial properties because part of the calcium in calcium phosphate is replaced with an antibacterial metal. The degree of substitution of the calcium in the calcium phosphate with the antibacterial metal (the mass of the antibacterial metal to be substituted / the mass of calcium) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and 5-10 weight% is still more preferable. However, it is technically difficult to completely replace all the metal ions charged at the time of synthesis into the hydroxyapatite structure, and a part of the charged metal ions is a fine particle of substituted calcium phosphate as a metal salt or a metal simple substance. You may adhere to the surface of.

(Antimicrobial metal)
Examples of the antibacterial metal include copper, silver, zinc, iron, lead, nickel, cobalt, palladium, and platinum. These may be used alone or in combination of two or more. Among these, copper, silver, and zinc are preferable and silver is more preferable from the viewpoint of improving the antibacterial and antiviral properties of the base material. By using calcium phosphate containing these antibacterial metals, an effect of killing viruses and various fungi and a deodorizing effect of adsorbing and decomposing hydrogen sulfide and ammonia are exhibited. In general, an antibacterial metal is rarely used alone, and in combination with a carrier such as calcium phosphate or an antibacterial improvement aid, it improves activity and sustainability, imparts sustained release, prevents discoloration, Improved chlorine resistance.

  As described above, the antibacterial metal preferably has 0.01 to 30% by mass of calcium in calcium phosphate substituted with an antibacterial metal, and 0.1 to 10% by mass is substituted. More preferably, 0.5 to 10% by weight is more preferably substituted. If the substituted antibacterial metal is less than 0.01% by mass, the antibacterial property of the obtained fiber is not sufficient, and if it exceeds 30% by weight, the antibacterial property of the obtained fiber is saturated, which is not economical. The substituted calcium phosphate may contain silver ions by a conventionally known method, for example, an ion exchange method, and may be heat-treated as necessary. This heating makes it difficult to elute as silver ions. In addition, some of the charged metal (ions) are deposited on the surface of calcium phosphate in the form of salts such as nitrates, nitrites, chlorates, perchlorates, acetates, sulfates, oxalates, and chlorides. It may be attached as a metal salt.

  Then, the manufacturing method of a composite base material is demonstrated. A method for producing a composite substrate is a fine particle arranging step in which fine particles of substituted calcium phosphate in which a part of calcium in calcium phosphate is replaced with an antibacterial metal are arranged on a coupling agent coated surface of a substrate coated with a coupling agent. including. In addition to the fine particle arranging step, it is preferable to further include a heating step of heating the substrate on which the fine particles are arranged, and the coupling agent is preferably alkoxysilane.

Moreover, it is preferable that the hydrolyzate of the alkoxysilane represented by General formula (1) or (2) is formed in a microparticle arrangement | positioning process and / or a heating process.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]

  As a method of applying the alkoxysilane hydrolyzate and the condensate thereof to the substrate, a spray method, a dip method, a roll coating method, a spin coating method, or the like is applicable. After coating, the silanol group generated at the same time as evaporation of the solvent by heating at a temperature of 20 to 200 ° C. becomes a bridging agent by joining the fine particles of substituted calcium phosphate and the substrate, Adhesive strength between the two is imparted.

  As a method of substituting a part of calcium ions in calcium phosphate with antibacterial metal ions to obtain a substituted calcium phosphate, a method performed at the time of synthesizing calcium phosphate, forming only calcium phosphate on the substrate in advance, and performing ion exchange later The technique to perform is mentioned. As the former, an aqueous solution in which calcium ions are dissolved during synthesis of calcium phosphate and an aqueous solution in which target metal ions are dissolved are mixed at a constant ratio, and a mixed solution containing two types of ions is mixed with an aqueous solution containing phosphate ions. By reacting with calcium phosphate particles, calcium phosphate fine particles in which some of the calcium ions are substituted with other metal ions can be precipitated. As the latter (introduction by ion exchange), a calcium phosphate fine particle is combined with a hydrolyzate of alkoxysilane and / or its condensate, and then a composite base material in which calcium phosphate is adhered to an aqueous solution in which a target metal salt is dissolved is used. Ion exchange is performed by immersion. The aqueous solution can be prepared using nitrate, nitrite, chlorate, perchlorate, acetate, sulfate, oxalate, chloride, or the like.

  To place the fine particles of substituted calcium phosphate on the surface of the base material where the coupling agent is applied, first adjust the pH in an alkaline environment containing calcium ions and antibacterial metal ions in a metal, plastic, glass, or other container. The base material in which the thin film by the aqueous solution and the hydrolyzate of alkoxysilane and / or its condensate was formed is put. Next, an aqueous solution containing phosphate ions is dropped, and the pH in the aqueous solution after mixing is adjusted to 7 or more and a desired Ca / P ratio. After adjusting the aqueous solution, the solution is sufficiently mixed by shaking the container and allowed to stand for 1 to 24 hours. In this case, an aqueous solution containing phosphate ions and a substrate whose pH is adjusted by changing the order of addition may be added, and an aqueous solution containing calcium and metal ions having antibacterial properties may be added later. Moreover, you may add all the solutions containing each ion simultaneously. The point here is that the solution in contact with the substrate is adjusted to be alkaline in order to prevent oxidation of the substrate, and the pH of the aqueous solution after mixing the solution is always 7 or higher.

  The calcium source is not particularly limited as long as it is derived from a calcium compound. Specific examples include calcium salts of inorganic salts such as calcium hydroxide, calcium salts of inorganic acids such as calcium nitrate, and calcium salts of organic acids such as calcium acetate. Examples of the phosphoric acid source include phosphoric acid, phosphates such as ammonium dihydrogen phosphate and diammonium hydrogen phosphate, and condensed phosphoric acids such as pyrophosphoric acid (diphosphoric acid) and metaphosphoric acid. That is, any phosphate compound may be used as long as it can be precipitated by reacting a salt that gives calcium ions (nitrate, acetate, carbonate, sulfate, chloride, hydroxide) with phosphate ions. Among these, in consideration of impurities to be mixed, those deposited using an ammonium phosphate salt are particularly good.

The reaction solution for forming calcium phosphate is preferably a neutral region to a basic region. Deposition (oxidation) of the substrate can be prevented by precipitation in a neutral to basic region. Moreover, it is preferable that the reaction solution at the time of especially forming a hydroxyapatite among calcium phosphates is pH 7 or more also considering the solubility product of calcium phosphates, More preferably, it is 8-11. Hydroxyapatite dissolves in the acidic region, and calcium phosphate other than hydroxyapatite precipitates and mixes in the neutral region. For pH adjustment, a base such as aqueous ammonia, sodium hydroxide, or potassium hydroxide can be used.
(Applied products)

  Composite substrates are not only medical materials that require biocompatibility, but also materials that use adsorbed components such as proteins and oils, filters that collect viruses, bacteria, animal and plant cells, etc. in liquids and gases, and waste liquid treatment. And can be applied to air cleaning filters and deodorizing antibacterial filters. In addition, since the composite base material is excellent in flexibility, strength, adhesion to a living body, and biocompatibility, it is for medical use such as percutaneous catheters, percutaneous medical devices such as percutaneous terminals, artificial blood vessels, artificial organs such as artificial organs, and the like. It can also be suitably used as a material. A composite base material using a film as a base material can be applied to various applications requiring antibacterial properties such as building materials, agricultural sheets, and various protective films as antibacterial films.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
<Example 1>
61.5 g of tetramethoxysilane was put in 1 L (liter) of a four-necked round bottom flask, 463.9 g of MeOH was added, and the mixture was stirred while keeping the liquid temperature constant at 30 ° C. Next, an aqueous solution obtained by adding 1.0 g of H ₃ PO ₄ (1M) to 71.6 g of water was added, and the mixture was stirred at 30 ° C. for 5 hours. This tetramethoxysilane hydrolyzate and isopropyl alcohol were mixed and adjusted so that the solid concentration was 5% by mass.
Next, a cotton woven fabric (50 mm × 50 mm × 1 mm thickness, about 0.45 g) was selected as the base material, and the whole base material was immersed in 100 ml of the tetramethoxysilane hydrolyzed solution. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. When the weight of the woven fabric after heating was measured, an increase of 2.2% was observed.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by replacing 10% of Ca in hydroxyapatite with Ag was formed on the surface of a cotton woven fabric coated with the tetramethoxysilane hydrolyzate. That is, a cotton woven fabric was placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm). (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution A mixed solution of 1.1 mL, (C) 25% by mass ammonia water 0.5 mL, and (D) pure water 20 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 3 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 10 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached cotton woven fabric in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Example 2>
An Ag-substituted hydrosiapatite-attached cotton woven fabric was prepared in the same manner by changing the tetramethoxysilane of Example 1 to a methoxysilane oligomer. That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat Co., Ltd., methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, then H ₃ PO ₄ (1M) 1 0.0 g was added and stirred for 5 hours. In this way, a hydrolyzate having a solid content concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass.
Next, the same cotton woven fabric (50 mm × 50 mm × 1 mm thickness, about 0.45 g) as in Example 1 was immersed in 100 ml of the hydrolyzed methoxysilane oligomer. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The heated woven fabric was slightly harder than Example 1, and the weight increase was 2.6%.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the surface of the hemp cloth coated with the methoxysilane oligomer hydrolyzate. That is, a cotton woven fabric was placed in a polypropylene container (outer dimensions: 167 mm × 117 × 28 mm), (A) 13.5 mL of 0.358 M calcium nitrate aqueous solution, (B) 1.1 mL of 1.0 M silver nitrate aqueous solution, (C) A mixed solution of 25% by mass of ammonia water (0.5 mL) and (D) pure water (20 mL) was added. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 3 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 5 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached cotton woven fabric in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Example 3>
A composite substrate was prepared in the same manner as in Example 2 except that the substrate was changed from cotton woven fabric to hemp fabric. That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. In this way, a hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass.
Next, a hemp cloth (50 mm × 50 mm × 1 mm thickness, about 0.45 g) was selected as the base material and immersed in 100 ml of the hydrolysis solution of the methoxysilane oligomer. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in the weight of the hemp fabric after heating was 2.6%.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the surface of the hemp cloth coated with the methoxysilane oligomer hydrolyzate. That is, a hemp cloth is placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm). (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution A mixed solution of 1.1 mL, (C) 25% by mass ammonia water 0.5 mL, and (D) pure water 19 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 10 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached linen cloth in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Example 4>
A composite substrate was prepared in the same manner as in Example 2 except that the substrate was changed from a cotton woven fabric to a woven fabric made of synthetic fibers (polyethylene 100%). That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. Thus, a methoxysilane oligomer hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass.
Next, a polyethylene woven fabric (50 mm × 50 mm × 1 mm thickness, about 0.40 g) was selected as a base material and immersed in 100 ml of the hydrolyzed liquid of methoxysilane oligomer (5 mass% solid content concentration). After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in weight of the base material after heating was 2.4%.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the surface of a polyethylene woven fabric coated with the hydrolyzate of the methoxysilane oligomer. That is, a woven fabric was placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm), (A) 13.5 mL of 0.358 M calcium nitrate aqueous solution, (B) 1.0 M silver nitrate aqueous solution 1 A mixed solution of 1 mL, (C) 25 mass% ammonia water 0.5 mL, and (D) pure water 19 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 5 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached polyethylene woven fabric in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Example 5>
A 10% Zn-substituted hydroxyapatite-coated linen fabric in which 10% of Ca in hydroxyapatite was substituted with Zn was produced. That is, the solid content concentration was adjusted to 5% by mass using a methoxysilane oligomer in the same manner as described in Example 3.
Next, the entire substrate was immersed in 100 mL of the methoxysilane oligomer hydrolyzate using hemp cloth (50 mm × 50 mm × 1 mm thickness, approximately 0.45 g) as the substrate. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in weight of the base material after heating was 2.4%.
Subsequently, a hemp-derived woven fabric (50 mm × 50 mm × 1 mm thickness, mass of about 0.45 g) is placed in a plastic container, and (A) 13.5 mL of a 0.358M calcium nitrate aqueous solution, (B) 1. A mixed solution of 0.54 mL of 0M zinc nitrate aqueous solution, (C) 0.5 mL of 25 mass% ammonia water, and (D) 20 mL of pure water was added (mixing order is not required). Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After standing for 3 hours, the woven fabric was taken out of the container with tweezers, and washed with pure water and acetone in this order. The washed woven fabric was dried under reduced pressure in a desiccator at room temperature. As described above, a Zn-substituted hydroxyapatite-attached linen cloth in which 10% of Ca in hydroxyapatite was substituted with Zn was obtained.

<Example 6>
Subsequently, an Ag-substituted hydroxyapatite-coated linen fabric in which Ca in hydroxyapatite was replaced with Ag using ion exchange was produced. That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. Thus, a methoxysilane oligomer hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass.
Next, a hemp cloth (50 mm × 50 mm × 1 mm thickness, about 0.45 g) was selected as the base material and immersed in 100 ml of the hydrolyzed methoxysilane oligomer. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in the weight of the substrate after heating was 2.6%.
The hemp cloth coated with the hydrolysis solution of the methoxysilane oligomer is placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm), and (A) 15 mL of a 0.358 M aqueous calcium nitrate solution ( B) A mixed liquid of 25 mL of 25% by mass ammonia water and (C) 20 mL of pure water was added. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was immersed in 100 mL of 0.1 M silver nitrate aqueous solution for about 5 hours. Thereafter, the woven fabric was taken out from the tweezers, and the woven fabric was washed in the order of pure water and acetone. As described above, an Ag-substituted hydroxyapatite-attached linen cloth was obtained by ion exchange of Ca ²⁺ and Ag ⁺ in an aqueous silver nitrate solution.

<Example 7>
The tetramethoxysilane of Example 1 was changed to methacrylic silane to prepare a methacrylic silane hydrolyzate, and the same treatment was performed on the PET film. That is, 61.5 g of methacryloxypropyltrimethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was placed in a 1 L (liter) four-necked round bottom flask, 463.9 g of MeOH was added, and the liquid temperature was kept constant at 30 ° C. While stirring. Next, 1.0 g of H ₃ PO ₄ (1M) was added to 71.6 g of water, and the mixture was further stirred at 30 ° C. for 5 hours. Isopropyl alcohol was added to the resulting methacrylsilane hydrolyzate to give a concentration of 5 It adjusted to the mass%.
Next, a PET film (A4100, 100 mm × 150 mm × 125 μm thickness, manufactured by Toyobo Co., Ltd.) was selected as the substrate, and the entire substrate was immersed in 100 mL of the methacrylic silane hydrolysis solution. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in weight of the substrate after heating was 2.5%.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the surface of the hemp cloth coated with the methacrylic silane hydrolyzate. That is, a PET film was placed in a polypropylene container (outer dimensions: 167 mm × 117 × 28 mm), and (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution 1.1 mL, ( C) A mixed liquid of 25 mL of 25% by mass aqueous ammonia and (D) 19 mL of pure water was added. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the PET film was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 5 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached composite film in which 10% of Ca in hydroxyapatite was substituted with Ag was produced.

<Example 8>
A composite base material was produced in the same manner as in Example 2 by changing the base material to a glass plate (BK-5 glass substrate, manufactured by Matsunami Co., Ltd., 25 mm × 75 mm × 0.7 mm thickness). That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. Thus, a methoxysilane oligomer hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass. The increase in weight of the substrate after heating was 2.5%.
Next, the glass plate was immersed in 100 ml of the hydrolyzed methoxysilane oligomer. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by replacing 10% of Ca in hydroxyapatite with Ag was formed on a glass plate coated with the hydrolyzate of the methoxysilane oligomer. Specifically, a glass plate was placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm). (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution 1 A mixed solution of 1 mL, (C) 25 mass% ammonia water 0.5 mL, and (D) pure water 19 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the glass plate was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the glass plate was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The glass plate after washing was heat-dried at 120 ° C. for 5 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached glass plate in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Example 9>
A composite substrate was prepared in the same manner as in Example 2 except that the substrate was changed to an acrylic resin plate (Sumitomo Chemical Co., Sumipex, 100 mm × 150 mm × 1 mm thickness). That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. Thus, a methoxysilane oligomer hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the concentration to 5% by mass.
Next, the acrylic resin plate was immersed in 100 ml of the methoxysilane oligomer hydrolysis solution. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes. The increase in weight of the substrate after heating was 2.5%.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the glass plate surface coated with the methoxysilane oligomer hydrolyzate. That is, an acrylic resin plate is placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm). (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution A mixed solution of 1.1 mL, (C) 25% by mass ammonia water 0.5 mL, and (D) pure water 19 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the acrylic resin plate was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the glass plate was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed acrylic resin plate was heat-dried at 120 ° C. for 5 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached acrylic resin plate in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Comparative Example 1>
Ag-substituted hydroxyapatite was formed on the substrate surface without coating the substrate surface with an alkoxysilane hydrolyzate. That is, a hemp cloth is placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm). (A) 0.358 M calcium nitrate aqueous solution 13.5 mL, (B) 1.0 M silver nitrate aqueous solution A mixed solution of 1.1 mL, (C) 25% by mass ammonia water 0.5 mL, and (D) pure water 20 mL was charged. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the hemp cloth (50 mm × 50 mm × 1 mm thickness, about 0.45 g) was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed linen fabric was heat-dried at 120 ° C. for 10 minutes in a high-temperature bath. As described above, an Ag-substituted hydroxyapatite-attached linen cloth in which 10% of Ca in hydroxyapatite was substituted with Ag was obtained.

<Comparative example 2>
A hydroxyapatite-attached linen fabric was prepared in the same manner as in Example 2 without replacing Ca in hydroxyapatite with Ag. That is, 60 g of a methoxysilane oligomer (manufactured by Colcoat, methyl silicate 51) was placed in a 300 ml three-necked round bottom flask, 33 g of MeOH was added, and the mixture was stirred at 25 ° C. to make the solution uniform, and then H ₃ PO ₄ (1M). 1.0 g was added and stirred for 5 hours. Thus, a methoxysilane oligomer hydrolyzate having a silane concentration of 30% was obtained. Isopropyl alcohol was added to the methoxysilane oligomer hydrolyzate to adjust the silane concentration to 5% by mass.
Next, a hemp cloth (50 mm × 50 mm × 1 mm thickness, about 0.45 g) was selected as the base material and immersed in 100 ml of the hydrolysis solution of the methoxysilane oligomer. After soaking for about 10 seconds, the substrate was pulled up, the excess solution was shaken off, and heated at 80 ° C. for 3 minutes.
Subsequently, 10% Ag-substituted hydroxyapatite obtained by substituting 10% of Ca in hydroxyapatite with Ag was formed on the surface of the hemp cloth coated with the methoxysilane oligomer hydrolyzate. That is, a hemp cloth was placed in a polypropylene container (outside dimensions: length 167 mm × width 117 × height 28 mm), (A) 15 mL of 0.358 M calcium nitrate aqueous solution, (B) 25 mass% ammonia water 0. A mixed solution of 5 mL and (C) 20 mL of pure water was added. Subsequently, 15 mL of (E) 0.195M ammonium dihydrogen phosphate aqueous solution was dropped into the mixed solution in which the woven fabric was immersed.
(E) After dropping, the container was immediately sealed, and the container was shaken left and right several times and stirred. After leaving still for 5 hours, the woven fabric was taken out of the container with tweezers, and the woven fabric was washed in the order of pure water and acetone. The washed woven fabric was heat-dried at 120 ° C. for 10 minutes in a high-temperature bath. As described above, a hydroxyapatite-attached linen fabric was obtained.

<Test 1 (antibacterial test)>
According to the test method prescribed | regulated to JISL1902 (the antibacterial test method and antibacterial effect of a textile product), antibacterial performance was investigated about Example 1- Example 7 and Comparative Example 1- Comparative Example 2. That is, using S. aureus (NBRC12732) with a viable count of 1.4 × 10 ⁵ cells / mL and E. coli (NBRC3972) with 2.6 × 10 ⁵ cells / mL, an untreated amount of 0.2 mL The cotton fabric (standard fabric) and the substrates obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were inoculated, and the number of bacteria on each woven fabric was measured after culturing at 35 ° C. for 18 hours.
Based on the number of bacteria on the unprocessed (cotton) fabric, the ratio of the number of bacteria on each woven fabric obtained in Examples 1 to 7 and Comparative Examples 1 and 2 is expressed as a logarithmic value, did. The results are shown in Table 1.

  From Table 1, the bacteriostatic activity value became zero or more in Examples 1 to 7 and excellent antibacterial properties were shown.

<Test 2 (Adhesive strength evaluation)>
Evaluation of the adhesive force between the base material / calcium phosphate in the composite base materials of Examples 1 to 10 and Comparative Examples 1 and 2 was performed by the following method using ultrasonic waves. The obtained composite base material was immersed in distilled water and treated with a probe type ultrasonic generator (Waken Pharmaceutical Co., Ltd .; model: W-220F) for 3 minutes under conditions of an output of 20 kHz and 35 W. The surface of the composite substrate after irradiation and drying was observed with a scanning electron microscope (SEM). FIG. 2 shows an SEM image (magnification 2000 times) of the composite substrate obtained in Example 1.

The weight loss of the composite substrate before and after the adhesion evaluation test (ultrasonic irradiation / drying) was measured. In the adhesion evaluation test, the case where the weight reduction of the calcium phosphate adhering to the base material is 0% to less than 10% is “◎”, the case where the weight reduction is 10% or more and less than 70%, “○”, the weight The adhesive force between the base material and calcium phosphate was evaluated by setting the case where the decrease was 70% or more and a majority of the fine particles were peeled off to be “x”.
Further, the particle diameter of the calcium phosphate fine particles remaining after the ultrasonic wave was measured with a scanning electron microscope (SEM). The average particle diameter was calculated by randomly selecting 20 remaining fine particles on the substrate and directly observing them. These evaluation results are shown in Table 2.
From Table 2, it was found that the use of a condensate such as methyl silicate 51 has a higher effect of improving the adhesive strength than that of a low-molecular substance such as tetramethoxysilane as alkoxysilane. This method was effective for both natural fibers and synthetic fibers, and was effective for woven fabrics, films, and glass plates as substrates. From this, since the peeling of the calcium phosphate fine particles having antibacterial properties from the base material is suppressed by providing the adhesive force between the substrate and the calcium phosphate fine particles, the antibacterial properties can be maintained for a long time.

Claims (23)

A substrate;
Fine particles of substituted calcium phosphate in which a part of calcium ions in calcium phosphate is substituted with antibacterial metal ions,
A composite substrate comprising a hydrolyzate of a coupling agent and / or a condensate thereof, which joins them.   The composite substrate according to claim 1, wherein the hydrolyzate of the coupling agent is a hydrolyzate of alkoxysilane. The fine particles are
Of calcium ions in calcium phosphate, 0.01 to 30% by mass is fine particles substituted with one or more metals selected from the group consisting of copper, silver, zinc, iron, lead, nickel, cobalt, palladium, and platinum. The composite substrate according to claim 1 or 2. The composite substrate according to claim 2 or 3, wherein the hydrolyzate of alkoxysilane is obtained by hydrolyzing an alkoxysilane represented by the general formula (1) or (2) in an alcohol solvent.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]   The total amount of the fine particles and the hydrolyzate of the coupling agent and / or the condensate thereof is 0.1 to 10% by mass with respect to the base material. The composite substrate as described.   The composite substrate according to any one of claims 1 to 5, wherein the calcium phosphate is hydroxyapatite.   The composite substrate according to any one of claims 1 to 6, wherein the substrate is any one of natural fibers, synthetic fibers, and glass fibers.   The composite substrate according to any one of claims 1 to 6, wherein the substrate is a polymer film.   The composite substrate according to any one of claims 1 to 6, wherein the substrate is a glass substrate.   A composite base material comprising a fine particle placement step of placing fine particles of substituted calcium phosphate in which a part of calcium ions in calcium phosphate are substituted with antibacterial metal ions on a coupling agent coated surface of a base material coated with a coupling agent Manufacturing method. The fine particle arranging step includes
The manufacturing method of the composite base material of Claim 10 which is the process of immersing the base material which apply | coated the said coupling agent in pH 7 or more aqueous solution containing a calcium ion, a phosphate ion, and an antimicrobial metal ion. The fine particle arranging step includes
A step of immersing the base material coated with the coupling agent in an aqueous solution of pH 7 or higher containing calcium ions and phosphate ions to dispose calcium phosphate fine particles on the surface;
In the calcium phosphate fine particles, the base material on which the calcium phosphate fine particles are arranged is immersed in an aqueous solution of at least one salt selected from the group consisting of nitrate, nitrite, chlorate, perchlorate, acetate and sulfate. And a step of substituting a part of the calcium ions with metal ions.   The manufacturing method according to claim 10, wherein the coupling agent is alkoxysilane.   The manufacturing method as described in any one of Claims 10-13 which further includes the heating process which heats the base material with which the said microparticles | fine-particles are arrange | positioned. In the heating step,
The manufacturing method of Claim 14 with which the hydrolyzate of the coupling agent represented by General formula (1) or (2) is formed.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]   The said heating process is a manufacturing method of the antimicrobial composite base material of Claim 14 or 15 which is a process of heating the base material in which the calcium-phosphate fine particle has been arrange | positioned at 20-200 degreeC. In the fine particle arranging step,
The manufacturing method as described in any one of Claims 10-16 in which the hydrolyzate of the coupling agent represented by General formula (1) or (2) is formed.
Si (OR) ₄ (1)
R ′ _n —Si (OR) _4-n (2)
[Wherein, R represents an alkyl group, R ′ represents a monovalent organic group, and n represents an integer of 1 to 3, respectively. ]   The antibacterial member which consists of a composite base material as described in any one of Claims 1-9.   The antibacterial filter which consists of a composite base material as described in any one of Claims 1-9.   The mask which consists of a composite base material as described in any one of Claims 1-9.   The wallpaper which consists of a composite base material as described in any one of Claims 1-9.   The curtain which consists of a composite base material as described in any one of Claims 1-9.   A table cloth comprising the composite substrate according to any one of claims 1 to 9.