JP2652055B2 - Pack for preparing noble metal organosol and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pack for preparing a noble metal organosol and a method for producing the same, and the pack for preparing a noble metal organosol according to the present invention comprises plastics, fibers and inorganic substances. It is used for preparing a noble metal organosol used for dyeing or coloring such as.

[Conventional technology]

The color tone is cited as one standard of the commercial value of plastics, fiber molded products such as paper and non-woven fabric, and inorganic substances, etc., and dyeing or coloring to obtain a clear color tone is basically an essential condition. ing.

Conventionally, in dyeing or coloring plastics, fiber molded products such as paper and non-woven fabrics and inorganic substances,
Using a red or yellow transparent liquid gold or silver organosol (hereinafter referred to as a noble metal organosol), by applying or impregnating on the surface of various substances, and then evaporating a volatile organic solvent as a dispersion medium. A method has been proposed in which a gold or silver colloid is provided on the surface to obtain a clear color tone (Japanese Patent Application Laid-Open No. Sho 62-121640).

The noble metal organosol used for dyeing or coloring various substances, after forming an aggregated precipitate from the noble metal hydrosol, removing the aqueous solution portion by excess or decantation, or adding an organic solvent in the presence of the aqueous solution It is a solution that is redissolved.

[Problems to be solved by the invention]

In the production of the above-mentioned noble metal organosol, a step of coagulating and precipitating the noble metal hydrosol and then re-dissolving it in an organic solvent, or adding an organic solvent in the presence of an aqueous solution, and then separating an aqueous phase and an organic solvent phase It is considered that a special large-sized liquid separation device is indispensable for the step.

In addition, when a large amount of an organic solvent is used and a precious metal organosol is stored after production, a special container that is safe, resistant to organic solvents and is not corroded by the precious metal is required. Furthermore, it is necessary to pay attention to the safety of the process or the transportation of the noble metal organosol, and there is a problem that the handling is generally inconvenient.

An object of the present invention is to solve the above-mentioned problems.

[Means for solving the problem]

The present inventors have conducted intensive studies over a long period of time in order to solve the technical problem, and as a result, focused on a noble metal colloid obtained by coagulating and precipitating a noble metal hydrosol before re-dissolving with an organic solvent, The colloid particles were carried to obtain the supported material or the noble metal colloid particles recovered by the supported material, and then the loaded material or the noble metal colloid particles were charged into an organic solvent and recovered from the supported noble metal colloid particles or the supported material. If the noble metal colloid particles can be peptized in an organic solvent to prepare a noble metal organosol,
At the same time as the necessity of the conventional special large-sized liquid separation device in the production of the noble metal organosol is eliminated, the noble metal colloid particles supported by the noble metal colloid particles or the noble metal colloid particles recovered by the support do not contain an organic solvent. Therefore, it was thought that no special container was required for storage, and it was possible to further avoid paying special attention to safety, health, and transportation. Further, the inventor of the present invention came up with the idea of packing a noble metal colloid particle loaded on a noble metal colloid particle or a noble metal colloid particle recovered from the noble metal particle for easy handling, and completed the present invention.

That is, the present invention relates to a noble metal organosol preparation pack in which a carrier carrying gold or silver colloid particles, or one of gold colloid particles and silver colloid particles is sealed in a liquid-permeable pack material, and gold or silver. An electrolyte is added to the gold or silver hydrosol obtained by reducing the aqueous salt solution to cause the gold or silver colloid to coagulate and precipitate, and then separated using a material and washed with water to form a gold or silver colloid particle on the material. A noble metal organosol preparation pack, characterized in that the support is dried, and then the support is dried and the gold or silver colloid particles recovered by the support are encapsulated in a liquid pack material. .

[Action]

First, the most important point in the present invention is that a carrier carrying gold or silver colloid particles obtained by coagulating and precipitating a gold or silver hydrosol or a gold or silver colloid particle recovered by the carrier is a liquid-permeable packing material. It is in the point enclosed in. When the noble metal organosol preparation pack is used for dyeing or coloring various substances, the pack is put into a required organic solvent, and the gold or silver colloid particles supported on the carrier in the pack are charged. The gold or silver organosol can be prepared by pulverizing any of the colloidal gold particles and silver colloidal particles recovered from the carrier into an organic solvent. At this time, it can be covered with a desired amount of the organic solvent according to the amount of the pack used.

The silver organosol can also be used for providing a catalyst in electroless metal plating.

Next, conditions for implementing the present invention will be described.

The gold or silver hydrosol that is the starting material of the noble metal organosol preparation pack in the present invention can be prepared by the following method.

In the presence of one or more cationic, anionic and nonionic surfactants, an aqueous solution of a gold or silver salt, preferably an aqueous solution of chloroauric (III) acid or silver (I) nitrate, is treated with sodium borohydride, It is obtained by reduction treatment with a reducing agent such as dimethylamine borane or hydrazine.

Further, in order to form an aggregated precipitate from the gold or silver hydrosol obtained by the above method, a method of adding an electrolyte to the gold or silver hydrosol is used. As the electrolyte,
An aqueous solution or solid of a chloride, bromide, or nitrate of an alkaline earth metal such as calcium chloride, barium chloride, sodium bromide, and calcium nitrate can be solid. In this case, if the concentration of the electrolyte is at least 30 times the molar ratio of gold or silver, coagulation and precipitation can be performed.

The resulting coagulated sediment is filtered and washed with a Nutsche or the like to remove the aqueous solution portion, and the gold or silver colloid particles are supported on the material to be supported. Next, the material supporting the colloidal gold or silver particles is sealed in a dry carrier or the colloidal gold or silver particles recovered from the carrier to pass through a liquid-pack material to obtain a pack for preparing a noble metal organosol.

As the material, paper, a membrane filter, cloth, or the like can be used.

The drying temperature may be within a temperature range in which gold or silver metal is not oxidized and a temperature range in which the material is not burned.

The collection of the colloidal gold or silver particles from the carrier can be carried out by gently sifting the colloidal particles carried thereon, or by collecting the colloidal particles on the carrier using a spatula or the like.

In addition, as the liquid-permeable packing material, any material that can penetrate the organic solvent to be used and can be used if it is insoluble,
A pack material having a particularly high wet strength and a breathable material is preferable. For example, materials of paper and nonwoven fabric can be used.
In the case of paper, pulp with a relatively long fiber length, or pulp made of synthetic or semi-synthetic fibers, and in the case of non-woven fabric, fibers or semi-synthetic fibers made of synthetic resin (polyethylene, polypropylene, polyamide, etc.) Rayon, acetate, etc.) are preferred. The paper or nonwoven fabric may be manufactured by any conventional method, but not so tight or thick. For example, in terms of the basis weight, those having a range of 20 to 40 g / m ² are preferable.

Using the noble metal organosol preparation pack of the present invention,
In order to dye or color various substances, the pack is put into an organic solvent, and the gold or silver colloid particles supported on the carrier enclosed in the pack or the gold or silver colloid recovered from the carrier are collected. The particles are peptized to prepare a gold or silver organosol.

As a treatment method for peptizing the gold or silver colloid particles supported on the carrier or the gold or silver colloid particles recovered from the carrier, ultrasonic irradiation is preferable.

When preparing a gold or silver organosol, as a substance used as an organic solvent, hydrocarbons such as hexane and benzene, and halogen-substituted hydrocarbons such as chloroform can be used.

The noble metal organosol prepared using the noble metal organosol preparation pack of the present invention has an extremely stable dispersion state and is stored at room temperature in a transparent state without precipitation for a long period of several months or more without precipitation. it can.

〔Example〕

 Next, the present invention will be described with reference to examples and use examples.

Example 1 500 mg of cetylpyridium chloride was dissolved in 10 ml of pure water and diluted to 900 ml with pure water. The solution was added to 50 ml of an aqueous solution of 75.5 mg of sodium borohydride while stirring vigorously, and 50 ml of an aqueous solution of 0.5 mol of chloroauric acid (III) was added dropwise. Hydrosol 1 was obtained. Subsequently, 100 ml of a 100 mmol aqueous solution of calcium nitrate was added to the gold hydrosol to form a dark red precipitate, and then the mixture was washed with Nutsche and washed with water to support the colloidal gold particles on paper (No. 6). After drying the material at 60 ° C, the supported colloidal gold particles were scraped off using a spatula and collected from the supported material.
9 mg of colloidal gold particles were recovered.

The collected colloidal gold particles are applied to a tea bag filter paper (Heat Pack MW (Nippon Paper Industries Co., Ltd.) with a basis weight of about 20 g / m ^2.
Was sealed in a bag having a size of 3 cm × 4 cm and a string attached thereto, and the bag was heated and melt-bonded to obtain a gold organosol preparation pack.

Example 2 Cetylpyridium chloride (500 mg) was dissolved in pure water (10 ml) and diluted with pure water to 985 ml. The solution was added to 10 ml of an aqueous solution of 75.5 mg of sodium borohydride under vigorous stirring, and 5 ml of an aqueous solution of 0.5 mmol of silver (I) nitrate was added dropwise to the solution. was gotten. Subsequently, 200 ml of a 1 mol aqueous solution of calcium nitrate was added to the silver hydrosol to form a precipitate,
The silver colloid particles are supported on paper (No. 6) by washing with water and water with a Nutsche, and then the supported material is dried at 60 ° C., and then the supported silver colloid particles are lightly sieved off from the supported material. 490 mg of silver colloid particles were recovered.

The collected silver colloid particles are applied to a tea bag filter paper (Heat Pack MW (Nippon Paper Industries Co., Ltd.) with a basis weight of about 20 g / m ^2.
Was sealed in a bag having a size of 3 cm × 4 cm and a string attached thereto, and the mouth of the bag was heated and melt-bonded to obtain a silver organosol preparation pack.

Example 3 0.5 mmol of chloroauric acid (III) was dissolved in 5 ml of pure water, and 988 of pure water was dissolved.
Diluted to ml. While stirring this solution vigorously, an aqueous solution 2 of 100 mg of stearyltrimethylammonium chloride was added.
Then, 10 ml of an aqueous solution of 75.5 mg of sodium borohydride was added dropwise thereto, and the color of the solution rapidly changed to dark red, and a uniform and transparent gold hydrosol 1 was obtained. Subsequently, 100 mmol of barium chloride in 200 ml of an aqueous solution was added to the gold hydrosol to form a dark red precipitate.Then, gold colloid particles were supported on a membrane filter by washing with Nutsche and washing with water, and then dried at 80 ° C. As a result, a carrier carrying 0.15 g of colloidal gold particles was obtained. The obtained gold colloid particle-carrying material was attached with a string having a size of 3 cm × 4 cm obtained by using a tea bag filter paper (Heatron GS (manufactured by Nippon Paper Industry Co., Ltd.) with a basis weight of about 20 g / m ² . It was sealed in a bag, the mouth of the bag was heated and melt-bonded to obtain a gold organosol preparation pack.

Example 4 0.5 mmol of silver nitrate (I) was dissolved in 5 ml of pure water, and 988 ml of pure water was dissolved.
Diluted. While vigorously stirring the solution, add 2 ml of an aqueous solution of 100 mg of sodium dodecylbenzenesulfonate, and add 10 ml of an aqueous solution of 75.5 mg of sodium borohydride.
Upon dropping, the color of the solution rapidly changed to yellow-brown, and a uniform and transparent silver hydrosol 1 was obtained. Subsequently, 100 ml of a 500 mmol aqueous solution of calcium chloride was added to the silver hydrosol to form a yellow-brown precipitate, which was then washed with Nutsche and washed with water to support the silver colloid particles on paper (No. 6), and then dried at 70%. As a result, a support carrying 0.10 g of silver colloid particles was obtained.

The resulting silver colloidal particles supported material, biasing the cord in size of 3 cm × 4 cm of basis weight was obtained using a tea bag filter paper of approximately 40 g / m ² (Heat Packs MW (manufactured by Nippon Paper Co.) The resultant was sealed in a bag, and the mouth of the bag was heated and melt-bonded to obtain a silver organosol preparation pack.

[Use Example 1] One bag of the gold organosol preparation pack obtained in Example 1 was put into a container containing 100 ml of toluene,
After ultrasonic irradiation treatment was performed for 30 minutes to peptize the colloidal gold particles in the pack, the pack was pulled out to prepare a dark red transparent gold organosol containing toluene having a gold colloid concentration of 0.10 wt% as a dispersion medium.

Next, the gold organosol solution was applied on the surface of an aluminum oxide molded body (2.5 cm × 1.0 cm × 0.05 cm) with a brush, and then toluene was evaporated.

The surface of the obtained aluminum oxide molded body was colored red-purple with gold colloid.

The gold organosol prepared using the gold organosol preparation pack was uniform and transparent without precipitation even after about 6 months at room temperature.

[Use Example 2] One bag of the silver organosol preparation pack obtained in Example 2 was put into a container containing 100 ml of toluene,
After performing the ultrasonic irradiation treatment for 30 minutes to peptize the silver colloid particles in the pack, the pack was pulled out to prepare a yellow transparent silver organosol using toluene having a silver colloid concentration of 0.098 wt% as a dispersion medium.

Next, a polyester fiber (3 cm × 4 cm) was immersed in the silver organosol solution at room temperature for 1 minute, pulled up from the solution and air-dried to obtain a polyester fiber dyed yellow.

The silver organosol prepared by the silver organosol preparation pack was uniform and transparent without precipitation even after about 6 months at room temperature.

〔The invention's effect〕

When preparing a noble metal organosol using the noble metal organosol preparation pack according to the present invention, a step of coagulating and precipitating a noble metal hydrosol and then re-dissolving it in an organic solvent, as found in the preparation of a conventional noble metal organosol. In addition, a special large-sized liquid separation device required for a process for separating an aqueous phase and an organic solvent phase is unnecessary.

In addition, noble metal organosol preparation packs use no organic solvent at all, and even when manufactured in large quantities, are safe and sanitary for storage and transportation, and at the same time, have a predetermined amount of organic solvent in a predetermined amount. The noble metal organosol can be easily prepared by pulverizing the noble metal colloid particles or the noble metal colloid particles collected by the noble metal colloid particles or the noble metal colloid particles supported on the carrier by mechanical treatment such as ultrasonic waves. ,
It is convenient to carry and can withstand long-term storage.

Furthermore, when various substances are dyed or colored using the noble metal organosol prepared using the noble metal organosol preparation pack, beautiful colors can be easily imparted.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-121640 (JP, A) JP-A-2-48035 (JP, A) JP-A-2-48036 (JP, A) JP-A-2- 229544 (JP, A)

Claims (4)

(57) [Claims] (1) A pack for preparing a noble metal organosol, wherein a carrier carrying gold or silver colloid particles is enclosed in a liquid-pack material. 2. A pack for preparing a noble metal organosol, wherein a gold or silver colloid particle is enclosed in a liquid-pack material. 3. A gold or silver hydrosol obtained by reducing an aqueous solution of a gold or silver salt is added with an electrolyte to coagulate and precipitate the gold or silver colloid, and then separated using a material and washed with water. A method for producing a noble metal organosol preparation pack, comprising supporting gold or silver colloid particles on the material, subsequently drying the support, and enclosing the material in a liquid-permeable pack material. 4. A gold or silver hydrosol obtained by reducing an aqueous solution of a gold or silver salt is added with an electrolyte to coagulate and precipitate a gold or silver colloid, and then separated using a material and washed with water. Noble metal organosol preparation, comprising: supporting colloidal gold or silver particles on the material, subsequently drying the support, and enclosing the colloidal gold or silver particles recovered from the support in a liquid-pack material. Manufacturing method for packs.