JP6042702B2 - Method for producing polymer material containing colloidal gold - Google Patents

Description

  The present invention relates to a method for producing a polymer material containing a gold colloid and a polymer material containing a gold colloid produced by the method.

  Since colloidal gold absorbs different wavelengths depending on the particle size and shape of the colloid, the colloidal material containing gold colloids with various properties can be designed by controlling the particle size and shape of the gold colloid. Can do. For example, gold colloid has the property of generating heat when it absorbs light, so that the metal-containing colloid material can be applied to a drug release material triggered by heat.

  By the way, effective drug release using a drug release material is achieved by controlling the amount and timing of drug delivery to the affected area. As one of methods for enabling such control, use of a stimulus-responsive drug release material that can change the amount of drug retained and the permeability at a stimulus-responsive site in response to an external stimulus has been studied.

  In the stimulus-responsive drug release material, the drug release amount can be adjusted by controlling the type and amount of the external stimulus. In addition to this, when a stimulus-responsive drug release material is used, a more effective drug release behavior can be achieved by controlling the distribution of stimulus response sites in the material and the response intensity to the stimulus. Therefore, when using gold-containing colloidal material as one of the stimuli-responsive drug release materials, the gold colloid in the material is used as a stimulus-responsive site, the temperature of the gold colloid is increased by light irradiation, and the drug is released from its vicinity Can do.

  However, since gold colloid has a high surface energy and is very easy to aggregate, its particle size and shape are likely to change. Changes in the particle size and shape of the colloidal gold affect the properties of the colloidal gold. Thus, in the metal-containing colloidal material, it is important to stabilize the particle size and shape of the gold colloid by suppressing the aggregation of the gold colloid in order to express the desired properties of the gold colloid. As one means for preventing the aggregation of colloidal gold, a method of immobilizing the colloidal gold on a material is known.

  As a technique for immobilizing gold colloid to a material, methods described in Patent Documents 1 to 3 are known. The method described in Patent Document 1 is a material in which gold colloid is immobilized in a carrier by dispersing gold ions in a polymer or inorganic material carrier and then reducing the gold ions with sodium tetraborate. Is the way to get. In the method described in Patent Document 2, gold ions are dispersed in an ion exchange resin column, and then gold ions are reduced to gold colloids by amino groups on the surface of the ion exchange resin to form gold colloids on the surface of the ion exchange resin. Is the method. The method described in Patent Document 3 is a method for supporting a colloidal gold colloid in a gel made of linear polyethyleneimine simply and in a short time.

JP 2009-220017 A JP 2008-239801 A JP 2006-233290 A

  However, in the method described in Patent Document 1, sodium tetraborate used as a reducing agent is highly reactive, so that when it comes into contact with gold ions, a reduction reaction to gold colloid occurs instantaneously. Therefore, the method described in Patent Document 1 is a method in which it is difficult to control the fixing site and density of the colloidal gold in the material.

  The method described in Patent Document 2 has a problem that the density of gold colloid to be fixed cannot be arbitrarily determined because the reduction reaction of gold ions occurs uniformly on the entire surface of the ion exchange resin having a reducing group. In addition, since the reactivity of the reducing group is low and it takes about one day to fix the gold colloid, there is a problem that the carrier for fixing the gold colloid deteriorates during the reduction reaction.

  According to the method described in Patent Document 3, since the polyethyleneimine block polymer acting as a reducing agent reacts uniformly with gold ions while forming a gel, it is difficult to control the fixing site and density of the gold colloid. There's a problem.

  Therefore, since the methods described in Patent Documents 1 to 3 are methods for producing a metal-containing colloidal material in which the gold colloid is uniformly fixed in the material, the metal-containing colloidal materials produced by these methods are: When used as a stimulus-responsive drug release material, it is difficult to specifically control the site where the drug is released and the amount of drug released. Also, in the step of fixing the gold colloid, when the treatment with a reducing agent or heat is performed for a long time, the polymer that is a basic component of the material is likely to be yellowed, the optical properties of the material are impaired, the material As a result of the deterioration, the colloidal gold cannot be fixed stably for a long time.

  Therefore, the present invention can produce a metal-containing colloidal material containing a desired amount of gold colloid at a specific site in the material and / or a relatively short time compared to the methods described in Patent Documents 1 to 3. Thus, an object of the present invention is to provide a method for producing a gold-containing colloidal material, in which gold ions in the material can be formed into a gold colloid.

  The present inventors came to pay attention to a reducing agent in earnest research about the said subject. Then, if a reducing agent whose reducibility changes according to the external environment and a substance that can change the external environment, and if the change of the external environment can be controlled according to the characteristics of the substance, it can be placed around the reducing agent. I thought that a certain gold ion could be converted into gold colloid. As a result of further studies, it was found that the formation of colloidal gold from gold ions can be completed in a short time by coexisting another inorganic salt different from the gold compound. The present invention has been completed based on these findings.

That is, according to the present invention,
Reducing agent whose reducing ability changes according to pH; acid generator or base generator; gold compound; and part or all of a polymer material containing an inorganic salt different from the gold compound, acid generation treatment or base generation treatment To provide a method for producing a polymer material containing part or all of the gold colloid, which comprises the step of obtaining a polymer material containing part or all of the gold colloid.

According to another aspect of the invention,
An acid generator or a base generator; a gold compound; and an acid salt in part or all of a polymer material containing an inorganic salt different from the gold compound and having a reducing functional group whose reducing ability changes depending on pH Provided is a method for producing a polymer material partially or entirely containing a gold colloid, which comprises a step of obtaining a polymer material partially or entirely containing a gold colloid by performing a generation treatment or a base generation treatment.

  In the present invention, preferably, the reducing agent whose reducing ability changes depending on the pH is a primary functional, secondary, tertiary or quaternary amino group; a hydroxyl group; or the amino It is an organic compound having both a group and a hydroxyl group.

  In the present invention, preferably, the acid generator is a photoacid generator or a thermal acid generator.

  In the present invention, preferably, the photoacid generator is a sulfonium salt, an iodonium salt, or a nonionic photoacid generator.

  In the present invention, preferably, the inorganic salt is an alkali metal salt, an alkaline earth metal salt, or a metal salt of an earth metal.

  According to another aspect of the present invention, there is provided a polymer material partially or entirely containing a gold colloid produced by the method of the present invention.

  According to another aspect of the present invention, a reducing agent whose reducing ability changes according to pH for producing a polymer material partially or entirely containing gold colloid from the polymer material; acid generator or base generator A solution comprising an agent; a gold compound; and an inorganic salt different from the gold compound is provided.

  According to another aspect of the present invention, an acid generator for producing a polymer material partially or entirely containing a gold colloid from a polymer material having a reducing functional group whose reducing ability changes depending on pH Alternatively, a solution containing a base generator; a gold compound; and an inorganic salt different from the gold compound is provided.

  According to the method of the present invention, the gold colloid can be formed at any site and / or density in the material. As a result, the polymer material containing the gold colloid of the present invention in part or in whole can be applied to, for example, a temperature-responsive material containing a drug, and the release behavior of the drug can be arbitrarily controlled. Application to materials for drug delivery systems can be expected. In addition, the method of the present invention can complete the formation of colloidal gold in a short time, for example, within 60 minutes, so that yellowing and deterioration of the material can be suppressed.

FIG. 1 is a photograph of the polymer material to which the gold colloid obtained in Example 1 is fixed. FIG. 2 is a photograph of the polymer material to which the gold colloid obtained in Example 2 is fixed. FIG. 3 is a photograph of the polymer material to which the gold colloid obtained in Example 3 is fixed. FIG. 4 is a photograph of the polymer material to which the gold colloid obtained in Example 4 is fixed. FIG. 5 is a photograph taken of the polymer material to which the gold colloid obtained in Example 5 is fixed. FIG. 6 is a photograph of the polymer material obtained by fixing the gold colloid obtained in Example 6. FIG. 7 is a photograph of the polymer material to which the gold colloid obtained in Example 7 is fixed.

1. First Method of the Present Invention A first method of the present invention, which is a method for producing a polymer material containing a part or all of a gold colloid, comprises a reducing agent and an acid generator whose reducing ability changes depending on the pH in the vicinity. For a polymer material containing an agent or a base generator, a gold compound and an inorganic salt different from the gold compound, an acid or a base is generated from the acid generator or the base generator by an external stimulus, and the pH is changed. This is achieved by obtaining a gold-containing colloidal material from a polymer material by reducing a gold compound into a gold colloid by a reducing agent having reducibility in accordance with a change in pH. According to the method of the present invention, the colloidal gold can be formed at an arbitrary density at an arbitrary site of the polymer material by limiting the amount and location of the external stimulus to be applied.

  The first method of the present invention comprises a reducing agent whose reducing ability changes according to pH; an acid generator or a base generator; a gold compound; and a part of a polymer material containing an inorganic salt different from the gold compound or The process includes a step of obtaining a polymer material containing gold colloid in part or in whole by performing acid generation treatment or base generation treatment on the whole.

  The step of obtaining a polymer material containing a reducing agent whose reducing ability changes according to pH; an acid generator or a base generator; a gold compound; and an inorganic salt different from the gold compound is not particularly limited. A reducing agent whose reducing ability changes according to the above; an acid generator or a base generator; a gold compound; and a solution containing an inorganic salt different from the gold compound individually or two or more thereof, and then preparing the solution It can be obtained by immersing the polymer material therein or injecting the solution into the polymer material. Hereinafter, as one embodiment of the present invention, a reducing agent whose reducing ability changes according to pH; an acid generator or a base generator; a gold compound; and a solution containing an inorganic salt different from the gold compound (hereinafter referred to as “containing”). Ingredient solution ")) Reducing agent whose reducing ability changes depending on pH by immersing the polymer material in it; acid generator or base generator; gold compound; and inorganic salt different from the gold compound The obtaining of a polymer material containing

  The solvent used in preparing the component-containing solution may be any solvent that can dissolve the component and can be appropriately set by those skilled in the art depending on the content of the component. For example, water, methanol, ethanol, isopropanol, THF, dimethyl sulfoxide, dimethylformamide and the like can be mentioned. The said solvent may be used independently according to the solubility of a component, and may use 2 or more types together by a suitable density | concentration if necessary. For example, a mixture of 1-30 v% water: 99-70 v% methanol can be used to prepare the component solution.

  The reducing agent whose reducing ability changes according to pH is not particularly limited as long as the reducing strength changes according to the change in the surrounding environment. The reducing ability that changes depending on the pH is achieved by, for example, a reducing functional group. Therefore, as a preferable example of the reducing agent whose reducing ability changes depending on pH, as a reducing functional group, a primary, secondary, tertiary or quaternary amino group; a hydroxyl group; or any one of the above And a compound having an amino group and a hydroxyl group. A more preferable example of the reducing agent whose reducing ability changes depending on the pH is an organic compound having a reducing functional group.

Examples of the primary, secondary, tertiary or quaternary amino group include —NH ₂ , —NR ₁ R ₂ , —N ⁺ R ₁ R ₂ R ₃ (wherein R ₁ , R ₂ And R ₃ each independently represents a hydrogen atom or an alkyl group.). When R ₁ , R ₂ and R ₃ are alkyl groups, for example, they may be branched, straight-chain or cyclic alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. Since reduction | restoration property may fall with a disorder | damage | failure, the carbon number is 1-3, More preferably, it is 1-2.

  Specific examples of the reducing agent having an amino group as a reducing functional group include, but are not limited to, methylamine, ethylamine, dimethylamine, diethylamine, 2-methylaminoethane, trimethylamine, triethylamine, and polyamine. is not.

Examples of the compound having a hydroxyl group as a reducing functional group include those represented by R ₄ —OH. When R ₄ is an alkyl group, for example, it may be a branched, linear or cyclic alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms, but the reducibility is reduced due to steric hindrance. Therefore, the number of carbon atoms is preferably 1 to 3, more preferably 1 to 2.

  Specific examples of the reducing agent having a hydroxyl group as the reducing functional group include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, polyol and derivatives thereof.

  Specific examples of the reducing agent having an amino group and a hydroxyl group as a reducing functional group include aminomethanol, 2-aminoethanol, 2-methylaminoethanol, dimethanolamine, diethanolamine, trimethanolamine, 2-dimethylaminoethanol, methyl Examples include, but are not limited to, diethanolamine and polyaminol.

  The reducing agent whose reducing ability changes depending on the pH can be used in combination of two or more in addition to the single use. The amount of the reducing agent is not particularly limited, and the type of reducing agent and the desired gold colloid However, it is 1 to 50 mg / L, preferably 2 to 30 mg / L, and more preferably 5 to 20 mg / L with respect to the component-containing solution. If the blending amount of the reducing agent whose reducing ability changes depending on the pH is lower than 2 mg / L, the gold colloid formation reaction is slowed, and thus the desired gold colloid formation amount may not be obtained. On the other hand, when the concentration is higher than 30 mg / L, the reduction reaction rate is increased, so that it may be difficult to control the site and density of the formed gold colloid.

  The gold compound used in the present invention generates gold ions in a solution, and the gold ions undergo a reduction reaction with a reducing agent whose reducing ability changes according to pH to form a gold colloid to form a polymer material. Included in. The gold compound contains gold and a gold ion in addition to the compound containing gold, and examples thereof include tetrachloroauric acid, alkali metal tetrachloroauric acid, diethylamineauric acid trichloride, ethylenediamineauric acid, and the like. It is not limited to these. A gold compound may be used independently and may use 2 or more types together if necessary.

  The concentration of the gold compound used in the present invention can be appropriately set depending on the structure of the gold compound used, the structure of the polymer material containing the gold colloid, and the solvent. For example, the concentration in the component-containing solution is 0.5 mg / L. It is preferably used at ˜1000 mg / L, more preferably 50 g / L to 500 mg / L. If the concentration of the gold compound is less than 0.5 mg / L, since the concentration of the gold compound contained in the polymer material is low, the reduction reaction by the reducing agent whose reducing ability changes depending on the pH may not proceed rapidly. There is sex. In addition, when the concentration of the gold compound is 1000 mg / L or more, the concentration of the gold compound contained in the polymer material is excessive, so that the reduction reaction rate is fast and fine control of the reduction reaction is difficult. It becomes difficult to control the fixing site and density of the colloidal gold formed.

  In the present invention, an acid generator or a base generator is used for the purpose of changing the pH at and near the site where the reducing agent whose reducing ability changes depending on the pH. Acid generators and base generators include photoacid generators and photobase generators that generate acid and base by absorbing light of a specific wavelength, and heat that generates acid and base by applying heat above a predetermined level. There are acid generators and thermal base generators. In the method of the present invention, the amount of reduction to form a colloidal gold is controlled by using the amount of change in pH caused by the influence of acid or base generated by applying external stimuli such as light or heat. To do. The acid generator and the base generator used in the present invention can be used without particular limitation as long as they generate an acid or a base by an external stimulus.

Specific examples of photoacid generators include triarylsulfonium PF ₆ salt, triarylsulfonium SbF ₆ salt, ditertiary butylphenyliodonium PF ₆ salt, 2-nitrobenzaldehyde, 2,4,6-tris (trichloro And methyl) triazine. Specific examples of the thermal acid generator include bis (cyclohexylsulfonyl) diazomethane and bis (tertiarybutylsulfonyl) diazomethane. As the base generator, specifically, 9-ansilylmethyl N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperazine, guanidinium 2- (3-benzoylphenyl) propionate, 1-anthraquinone-2-yl) ethyl imidazole carboxylate and the like. However, the acid generator and the base generator are not limited to these.

The concentration of the acid generator and the base generator in the component-containing solution is not particularly limited as long as the desired gold colloid can be formed from the gold compound, and is, for example, 0.5 nM to 50 mM, preferably 1 nM. ~ 20 mM. If the concentration is 0.5 nM or less, the amount of protons generated by stimulation is small, and the reduction reaction of gold ions does not proceed efficiently. If the concentration is 50 mM or more, a large amount of protons are generated by stimulation, which causes deterioration of the polymer material and yellowing associated therewith.

  In the present invention, an acid generator is preferably selected because of its high sensitivity to external stimuli, but a photoacid generator or a photobase generator is more preferably used in consideration of the ease of controlling the stimulus to be applied. It is done.

  In the method of the present invention, an inorganic salt different from the gold compound is used for the purpose of promoting the fixation reaction of the colloidal gold. The inorganic salt can be arbitrarily selected from alkali metal salts, alkaline earth metal salts, and earth metal salts, and is not particularly limited. Specific examples of the inorganic salt include lithium chloride, lithium carbonate, lithium phosphate, lithium borate, lithium acetate, lithium sulfate, sodium chloride, sodium carbonate, sodium phosphate, sodium tetraborate, sodium borate, sodium carbonate, Sodium bicarbonate, sodium acetate, sodium sulfate, potassium chloride, potassium carbonate, potassium phosphate, potassium tetraborate, potassium borate, potassium acetate, potassium sulfate, magnesium chloride, magnesium carbonate, magnesium phosphate, magnesium borate, acetic acid Magnesium, magnesium sulfate, calcium chloride, calcium carbonate, calcium phosphate, calcium borate, calcium acetate, calcium sulfate, aluminum chloride, aluminum carbonate, aluminum phosphate, aluminum borate, acetic acid Aluminum, but like aluminum sulfate, sodium chloride is preferably used from ease of handling. Inorganic salts may be used alone or in combination of two or more.

  The concentration of the inorganic salt in the component-containing solution is not particularly limited, but is, for example, 0.01 g / L to 20 g / L, preferably 0.1 g / L to 10 g / L, more preferably 0.5 g / L. L to 5 g / L. When the concentration of the inorganic salt is less than 0.01 g / L, the formation rate of the gold colloid cannot be sufficiently accelerated, so that the gold colloid cannot be fixed at a desired site or density in the polymer material as the carrier. . When the concentration of the inorganic salt is 20 g / L or more, the gold colloid is formed at a site or density different from the target site or density due to excessive acceleration of the formation rate of the gold colloid. It becomes difficult to form a gold colloid at a desired site or density in a molecular material.

  When the gold colloid fixation reaction is carried out by the method of the present invention, it is preferable to control the pH in the carrier during colloid formation because the reaction rate of the fixation reaction varies depending on the amount of change in the pH inside the gold colloid fixation carrier. . When an acid generator is used, the pH inside the carrier is adjusted to 8.0 or more. When a base generator is used, the pH inside the carrier is adjusted to less than 7.5, thereby controlling the reaction rate of colloidal gold formation. It becomes possible to do.

  As a pH adjuster for maintaining the pH in the carrier at 8.0 or more, N-2-hydroxyethylpiperazinepropanesulfonic acid, tricine (N-trishydroxymethyl) methylglycine, glycinamide, glycylglycine, bicine, (N, N-bis (2-hydroxyethyl) glycine), tris (hydroxyethyl) methylaminopropanesulfonic acid, 4-aminopyridine, histidine, serine, borate, phosphate, ammonia, 3- (cyclohe Xylamino) ethanesulfonic acid, leucine, glycine, piperazine, carbonate, 3- (cyclohexylamino) propanesulfonic acid and the like.

  Examples of the pH adjuster for keeping the pH in the carrier below 7.5 are hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic acid, aniline, propionic acid, pyridine, uric acid, 2- (N-morpholino) ethanesulfonic acid, Examples include cacodylic acid, piperazine N, N′-bis (2-ethanesulfonic acid) N- (2-acetamido) -2-aminoethanesulfonic acid, and imidazole.

  The pH adjuster for adjusting the pH in the carrier to the pH described above may be used alone or in combination of two or more. As a specific example of the pH adjuster, borate can be used when an acid generator is used. The concentration of the pH adjusting agent is not particularly limited as long as it is an amount that can be adjusted to a predetermined pH. The inorganic salt and pH adjuster used in the method of the present invention can be substituted with a single compound, and a compound added for one purpose may be used for the other purpose.

  In addition to the first component consisting of a reducing agent whose reducing ability changes according to pH; an acid generator or a base generator; a gold compound; and an inorganic salt different from the gold compound, the component-containing solution has the above pH. Various compounds can be included as long as they do not impair the solution to the problems of the present invention, such as a regulator. In addition, the term “comprising” in the present specification means that an object is present as it is or in a non-limiting manner in contact with at least a part thereof, or retained, including, holding, The terms include, contain, have, have, fix, contact, etc. are interchangeable. In the component-containing solution, each component can be present uniformly or non-uniformly, and the solution may be clear or cloudy. The component-containing solution may be prepared immediately before carrying out the method of the present invention, or may be prepared in advance and stored under appropriate storage conditions.

  The immersion of the polymer material in the component-containing solution may be performed by immersing a part of the polymer material in the component-containing solution instead of the entirety of the polymer material. It is also achieved by contact.

  The polymer material used in the method of the present invention forms a gold colloid on the surface and / or inside thereof, and a reducing agent whose reducing ability changes depending on pH; acid generator or base generator; gold compound And any inorganic salt different from that of the gold compound is not particularly limited, but those having appropriate voids and characteristics for completely including these components are preferable. As the polymer material, a reducing agent whose reducing ability changes depending on pH, an acid generator or a base generator, a gold compound, and an inorganic salt different from the gold compound are easily included. A polymer gel obtained by polymerizing a monomer is preferably used. In addition to the polymerizable functional group, the monomer having a polymerizable functional group is a primary, secondary, tertiary or quaternary, like a reducing agent whose reducing ability changes according to pH. A monomer having a reducing functional group such as a secondary amino group or a hydroxyl group may be used. Examples of the monomer include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 3 -Hydroxypropyl (meth) acrylamide, dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meta ) Acrylate, dimethylaminomethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide (Meth) acrylamidopropyltrimethylammonium chloride, N, N-dimethylacrylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, (meta ) Hydrophilic monomers such as acrylic acid, N-vinylpyrrolidone, diethylene glycol dimethacrylate, polyethylene glycol monomethacrylate, glycerol methacrylate, tris (trimethylsiloxy) silylpropyl methacrylate, α, ω-di (methacryloxymethyl) polydimethyl Siloxane, α-mono (methacryloxymethyl) polydimethylsiloxane, α-mono (3-methacryloxypropyl) polydimethylsiloxane, α, ω-di (3-methacryloxypropyl) Hydrophobic monomers such as polydimethylsiloxane. These monomers may be used alone or in combination of two or more. However, in order for the obtained copolymer to form a polymer gel, it has at least one hydrophilic monomer as a constituent component. .

  In the case of using a monomer having a reducing functional group, the blending amount thereof is appropriately set depending on the desired amount of colloidal gold formed, and is not particularly limited. 30% is preferable, and 5 to 20% is more preferable. When the blending amount of the monomer having a reducing functional group is lower than 2%, the gold colloid formation reaction is delayed. In addition, when the blending amount of the monomer having a reducing functional group is higher than 30%, the reduction reaction rate is high and fine control of the reduction reaction of the gold colloid cannot be performed. It becomes difficult to control the formation site and density.

  A reducing agent whose reducing ability changes according to pH; an acid generator or a base generator; a gold compound; and a polymer material containing an inorganic salt different from the gold compound is a reducing agent whose reducing ability changes according to pH. An acid generator or a base generator; a gold compound; and an inorganic salt different from the gold compound in the form as it is or in a changed form, and is not particularly limited. The amount of the component contained in the polymer material may vary depending on the type of polymer material, the concentration and type of the component, and the like.

  In the method of the present invention, a polymer material containing gold colloid in part or in whole is obtained by subjecting part or all of the polymer material containing the above components to acid generation treatment or base generation treatment.

  The acid generation treatment or base generation treatment is carried out by applying an external stimulus to the acid generator or base generator contained in the polymer material to cause a change in pH in the polymer material. In the case where a photoacid generator or a photobase generator is included in the polymer material, external stimulation for acid generation treatment or base generation treatment is performed by light irradiation. When a thermal acid generator or a thermal base generator is included in the polymer material, external stimulus for acid generation treatment or base generation treatment is applied by heating. Since the amount of acid and base generated varies based on the wavelength and intensity of the light to be irradiated and the heating temperature, the irradiation conditions and heating conditions are appropriately selected according to the target gold colloid formation amount.

  When using a photoacid generator or a photobase generator, it is preferable to adjust the temperature in addition to light irradiation in consideration of the influence on the reduction reaction of the gold compound in the acid generation treatment or base generation treatment, For example, the temperature of the polymer material that is irradiated with light is set to a range of 50 ° C to 80 ° C. When the temperature is 50 ° C. or lower, the acid generated at the irradiated site may diffuse before the reduction reaction of the gold compound, so that no gold colloid is formed or a small amount of gold colloid can be formed at an unintended site. There is sex. In addition, when the temperature is 80 ° C. or higher, the reduction rate of the gold compound is excessively accelerated, and the reduction of the gold compound proceeds with a small amount of acid, so that the acid generated at the light irradiation site diffuses to a site other than the irradiation site. There is a possibility that colloidal gold is formed at a site other than the target site.

  Although it does not specifically limit as a specific example of an acid generation process and a base generation process, When using a photoacid generator or a photobase generator as a density | concentration in a component-containing solution at 0.5-10 mg / L, 50 ~ This is achieved by irradiating a polymer material heated to 80 ° C. with a UV lamp (80 to 320 watts) having a wavelength of 220 to 380 nm at a distance of 5 to 10 cm for 30 seconds to 5 minutes. When a thermal acid generator or a thermal base generator is used at a concentration of 0.5 to 10 mg / L in the component-containing solution, a metal plate heated to 50 to 80 ° C. is brought into contact with the polymer material for 30 seconds to 5 minutes. Is achieved.

  In the present invention, the means for forming the gold colloid in the polymer material at an arbitrary site is not particularly limited, and means for applying an external stimulus such as light and heat to a specific site of the target substance known in the art. Can be used. For example, by using a photomask at the time of light irradiation and designing the part where the polymer material that is the gold colloid carrier is not irradiated with light, the gold colloid is formed in the polymer material. Can be controlled. In addition, since the amount of acid and base generated can be controlled by adjusting the amount of light irradiation using a neutral density filter, the amount and density of colloidal gold formed by adjusting the reduction reaction Can be controlled.

  In the method of the present invention, considering the reactivity of the reducing agent whose reducing ability changes depending on the pH, operations other than the acid generation treatment or the base generation treatment are preferably performed at, for example, 60 ° C. or less. Perform at 30 ° C. or lower.

  Whether or not a polymer material containing a part or all of the gold colloid is obtained by the method of the present invention can be visually observed. That is, the gold colloid is colored from magenta to bluish purple according to the particle size and shape of the colloid by surface plasmon resonance, so if the polymer material after acid generation treatment or irradiation with base generation light is visually observed, The coloration can be observed at the portion where the colloidal gold is generated. Therefore, for example, if coloration can be confirmed in a part of the polymer material, it indicates that a polymer material containing a gold colloid in part is obtained. Further, the amount (density) of the gold colloid can be confirmed by the degree of color development. When the amount of colloidal gold is large, the color is dark, and when the amount is small, it is observed as a light color.

  The method of the present invention can include various steps in the former stage or the latter stage. For example, in order to remove surplus components, it is preferable to provide a cleaning step of cleaning a polymer material containing gold colloid partially or entirely with a cleaning liquid. The cleaning step can be performed, for example, by immersing a polymer material containing gold colloid in part or all in the cleaning liquid.

  When an acid generator is used, it is preferable to use a basic aqueous solution of 10 mM or more and pH 9 or more as a cleaning solution. This is because when an acidic solution is used as the cleaning liquid, the reduction reaction of the unreacted gold compound is promoted, and gold ions are reduced during the cleaning process, and an unintended gold colloid is formed. In addition, when pure water or dilute neutral or basic solution is used, an acid derived from the acid generator is dissolved in the aqueous solution, and the solution becomes acidic, so that colloidal gold may be formed.

2. Second Method of the Present Invention As another aspect of the method of the present invention, a reducing function whose reducing ability changes depending on the pH of the polymer material, excluding reducing agents whose reducing ability changes depending on the pH. A method is provided for relying on groups to achieve pH variation in polymeric materials.

  Therefore, the second method of the present invention comprises an acid generator or a base generator; a gold compound; and a reducing functional group that includes an inorganic salt different from the gold compound and whose reducing ability varies depending on pH. The method includes a step of obtaining a polymer material containing gold colloid in part or in whole by subjecting part or all of the polymer material to acid generation treatment or base generation treatment.

  The second method of the present invention uses a solution that does not contain a reducing agent whose reducing ability changes according to pH, and a polymer having a reducing functional group whose reducing ability changes as a polymer material. It can be carried out in the same way as the first method of the present invention except that the material should be selected.

3. Metal-containing colloidal polymer material and solution of the present invention Another aspect of the present invention is a polymer material partially or entirely containing the gold colloid produced by the first method or the second method of the present invention. Furthermore, a solution containing the components used by the first method and the second method of the present invention is also provided as another aspect of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only by this Example.

[Preparation of polymer material]
Each monomer mixture prepared as a uniform solution according to the formulation shown as “Gel formulation” in Table 1 was placed in a mold and irradiated with a white fluorescent lamp for 60 minutes at room temperature to carry out a polymerization reaction. The obtained polymer was immersed in a 100% methanol solution for 1 hour, and then immersed in distilled water overnight to obtain a polymer material.

[Preparation of metal ion solution]
In accordance with the formulation shown as “Solution formulation” in Table 1, each reagent was added and mixed and homogenized at room temperature to prepare each solution.

(Examples 1 to 5) Fixation of colloidal gold by light stimulation Each polymer material was shielded from light using a polymer material and a metal-containing ion solution (pH 9) prepared according to the formulations of Examples 1 to 5 shown in Table 1. It was immersed in each metal-containing ion solution below and allowed to swell in equilibrium. Next, a photomask from which the letters “SEED” were cut out was placed on the surface of the polymer material that had been swollen in equilibrium, the polymer material was heated to 70 ° C., and then irradiated with ultraviolet light for 30 seconds. When the photomask was removed after the light irradiation, reddish purple coloration was confirmed at the die-cut portion of the letters “SEED” irradiated with ultraviolet light. The coloration was confirmed not only on the surface of the polymer material irradiated with light but also on the inside and the back surface. Thereby, it was shown that the gold colloid was formed in the die-cut portion of the letter “SEED” in which the coloration in the polymer material was confirmed. The gold-containing colloidal polymer material is immersed in an aqueous solution adjusted to pH 9 with 1M sodium hydroxide overnight at room temperature to remove excess reagents, dried and photographed as shown in FIGS. .

(Example 6) Fixation of gold colloid by heat Using a polymer material and a metal ion solution (pH 9) prepared according to the formulation of Example 6 shown in Table 1, the polymer material was shielded from light with a light-containing ion solution. And soaked in equilibrium. Subsequently, a round metal plate heated to 70 ° C. was brought into contact with the surface of the equilibrium swollen polymer material for 30 seconds. Then, when the metal plate was removed and visually confirmed, a reddish purple color was confirmed in the shape of the metal plate. Thereby, it was shown that the gold colloid was formed in the round shape part in which the coloration in the polymer material was confirmed. This gold-containing colloidal polymer material is immersed in an aqueous solution adjusted to pH 9 with 1M sodium hydroxide overnight at room temperature to remove excess reagents, dried, and photographed.

(Example 7) Production of polymer material in which colloidal gold was fixed in an inclined manner Polymer material was prepared using a polymer material prepared according to the formulation of Example 3 shown in Table 1 and a metal-containing ion solution (pH 9). It was immersed in the solution under light shielding and allowed to swell equilibrium. Next, a photomask with the letters “SEED” cut out is placed on the surface of the polymer material that has been swelled in equilibrium, and the light transmittance is reduced by 50% on the left two letters “SE” of the photomask. After covering the filter, the polymer material was heated to 70 ° C. and then irradiated with ultraviolet light for 30 seconds. When the polymer material irradiated with ultraviolet light was allowed to stand for 1 hour and then visually observed, a reddish purple color was confirmed in the portion irradiated with ultraviolet light. However, the portion where the neutral density filter was applied was less colored than the portion where the neutral density filter was not covered. As a result, it was shown that the colloidal gold was formed in the part of the polymer material where coloration was confirmed, and that the density of the colloidal gold fixed could be controlled by adjusting the amount of irradiation light. It was done. This gold-containing colloidal polymer material is immersed in an aqueous solution adjusted to pH 9 with 1M sodium hydroxide overnight at room temperature to remove excess reagents, dried and photographed, as shown in FIG.

(Comparative Example 1) Fixation of colloidal gold without using an inorganic salt different from chloroauric acid A polymer material and a metal-containing ion solution (pH 9.0 with sodium hydroxide) prepared by the formulation of Comparative Example 1 shown in Table 1 The polymer material was immersed in a metal ion solution under light shielding to cause equilibrium swelling. The surface of the polymer material that had undergone equilibrium swelling was covered with a photomask from which the letters “SEED” had been cut, and the polymer material was heated to 70 ° C. and irradiated with ultraviolet light for 30 seconds. However, a reddish purple color indicating the formation of colloidal gold was not confirmed on the surface of the polymer material after light irradiation.

(Comparative Example 2) Fixation of gold colloid in polymer material using sodium borohydride Using a polymer material prepared by the formulation of Comparative Example 2 shown in Table 1 and a metal ion solution (pH 9.0) The polymer material was immersed in a metal-containing ion solution under light shielding and allowed to swell equilibrium. By immersing the obtained polymer material in a 10 mg / L sodium borohydride aqueous solution, a reddish purple color was instantaneously confirmed throughout the polymer material. In this method, the colloidal gold cannot be fixed at any part of the polymer material, and the amount of the colloidal gold immobilized cannot be controlled.

  As shown in the above examples and comparative examples, a polymer material capable of controlling the formation site and the amount of colloidal gold according to external stimuli is manufactured, and a part of the gold colloid is produced by using this polymer material. Alternatively, it was possible to produce a polymer material including all of them. Furthermore, the gold colloid formation time is as short as about 30 seconds, and even if all the steps are combined, it is a very short time of about 5 to 60 minutes.

Abbreviations in Table 1 are as follows:
HEMA; 2-hydroxyethyl methacrylate NVP; N-vinylpyrrolidone DMAEA; dimethylaminoethyl acrylate MAPTAC; methacrylamidopropyltrimethylammonium chloride ED; diethylene glycol dimethacrylate
Tris; Tris (trimethylsiloxy) silylpropyl methacrylate

Claims (10)

Reducing agent whose reducing ability changes according to pH; acid generator or base generator; gold compound; and part or all of a polymer material containing an inorganic salt different from the gold compound, acid generation treatment or base generation treatment A process for producing a polymer material containing a colloidal gold part or all, comprising a step of obtaining a polymer material partly or entirely containing a gold colloid by applying An acid generator or a base generator; a gold compound; and an acid salt in part or all of a polymer material containing an inorganic salt different from the gold compound and having a reducing functional group whose reducing ability changes depending on pH A method for producing a polymer material partially or entirely containing a gold colloid, comprising a step of obtaining a polymer material partially or entirely comprising a gold colloid by performing a generation treatment or a base generation treatment. The reducing agent whose reducing ability changes according to the pH has, as a reducing functional group, a primary, secondary, tertiary or quaternary amino group; a hydroxyl group; or both the amino group and the hydroxyl group. The method according to claim 1, which is an organic compound. The method according to claim 1, wherein the acid generator is a photoacid generator or a thermal acid generator. The method according to claim 4, wherein the photoacid generator is a sulfonium salt, an iodonium salt, or a nonionic photoacid generator. The method according to claim 1, wherein the inorganic salt is an alkali metal salt, an alkaline earth metal salt, or a metal salt of an earth metal. A polymer material comprising the polymer material according to the following (1) or (2) partially or entirely containing a gold colloid.
(1) A reducing agent whose reducing ability changes depending on pH; an acid generator or a base generator; a gold compound; and a polymer material containing an inorganic salt different from the gold compound
(2) an acid generator or a base generator; a gold compound; and a polymer material having an inorganic salt different from the gold compound and having a reducing functional group whose reducing ability changes according to pH A reducing agent whose reducing ability varies depending on pH; an acid generator or a base generator; a gold compound; and a gold compound for producing a polymer material partially or wholly containing gold colloid from the polymer material; Are solutions containing different inorganic salts. an acid generator or a base generator for producing a polymer material partially or wholly containing a gold colloid from a polymer material having a reducing functional group whose reducing ability changes depending on pH; a gold compound; A solution containing an inorganic salt different from a gold compound. The polymer material according to the following (1) or (2) .
(1) A reducing agent whose reducing ability changes depending on pH; an acid generator or a base generator; a gold compound; and a polymer material containing an inorganic salt different from the gold compound
(2) an acid generator or a base generator; a gold compound; and a polymer material having an inorganic salt different from the gold compound and having a reducing functional group whose reducing ability changes according to pH