JPH10266010A - Carbonization treated powder of silky material, carbonization treated material and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To utilize a silk waste, a cut cocoon, etc., which have been disposed and produce the subject powder by housing a silky material in a baking furnace, drying the silky material into a bone-dry state, sealing an inert gas therein, heating the silky material, carrying out the carbonizing treatment thereof, then cooling the carbonized material and subsequently pulverizing the cooled material with a pulverizer. SOLUTION: A silky material such as a silk waste, a cut cocoon or a silk noil is housed in a hermetically sealable baking furnace and dried into a bone- dry state and an inert gas such as nitrogen gas or helium gas under 1-20 atm is then sealed therein to heat the silky material at 230-350 deg.C for 5-60 min to carry out the carbonizing treatment thereof. The carbonized material is subsequently cooled to ambient temperature and then crushed with a pulverizer so as to afford 0.1-10 μm particle diameter. Thereby, the objective fine particulate powder having residual characteristics of silk proteins is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various silk materials,
For example, conventionally-discarded wild silkworms, sub-silk yarns and the like generated from sericulture (selected cocoons, debris from the yarn-making process or weaving process), cocoons after cutting pupae (cut cocoons), cotton, silk noil, Wraps, slivers, fine swarf obtained by processing and carbonizing and shredding swarf of silk fabric or silk knitting, or used silk products (referred to as silk material) under predetermined conditions. The present invention relates to a carbonized powder, a carbonized product, and a method for producing the same of a silk material that can be used for materials such as paints, pharmaceuticals, activated carbon and the like.

[0002]

2. Description of the Related Art Silk has been used for silk fabrics and the like since ancient times. It is light, warm and comfortable, does not interfere with human skin respiration, helps regulate temperature and humidity, has excellent heat-retaining effects, has allergies and skin disorders. It has been widely used as a garment material having the property of not causing bleeding. In addition, the cocoon itself is used in various fields such as water purification and plant growth. However, other than the silk used as silk products, for example, the above-mentioned sub-silk yarn, various cutting chips such as cut cocoons and silk fabrics, and silk materials such as used silk fiber spliced products are almost discarded at present. ing.

[0003]

As described above, the most discarded silk materials have been studied for various effective uses, but they are still insufficient. It is said that proteins contained in silk and various amino acids constituting the same, such as alanine, are effective as pharmaceuticals for improving liver function, glycine and serine lower blood cholesterol levels, and tyrosine prevents dementia. By providing silk powder from which these various amino acids can be effectively extracted, the silk powder can be used as a raw material for pharmaceuticals or medical products. In addition, silk materials are generally characterized by a slight pearly luster and luster upon exposure to light, and it is expected that a new color tone will be obtained by finely crushing the silk material and blending it into paints, cosmetics, etc. . Furthermore, since the silk material has a shape close to that of a hollow fiber, the carbon fiber is directly carbonized and pulverized to obtain a porous carbon powder, which has an excellent adsorption function as compared with conventional coconut shell activated carbon. Activated carbon is expected.

[0004] The present invention provides a material that makes full use of the inherent properties of these silk materials while effectively utilizing the silk materials to be disposed of.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the carbonized powder of the silk material of the present invention is prepared by placing the silk material in a sealable firing furnace and drying it in a completely dry state. 1 to
An inert gas such as nitrogen gas or helium gas at 20 atm is sealed, heated at 230 to 350 ° C. for 5 to 60 minutes, carbonized, cooled to room temperature, and then ground by a pulverizer. Fine particle powder obtained by crushing so as to have a diameter of 0.1 to 10 μm, which retains the characteristics of silk protein.

[0006] Silk thread scraps produced from a silk product manufacturing plant,
Since silk materials such as cutting waste of silk fabrics and knitted fabrics, crushed pieces thereof, and powders usually contain 12% of the total weight of water, firstly, in order to be suitable for pulverization, the water of the materials is first removed. It must be skipped and kept dry. For example, it is dried at 100 to 150 ° C. for about 10 minutes.

[0007] Silk materials, particularly silk materials which have not undergone a kneading step occurring before the spinning step, are in a state in which a fibroin is coated with a cesiline layer, and when heated in an inert atmosphere, some of these proteins are decomposed and carbonized. A gray to brown product is obtained. By enclosing the inert gas, it is possible to prevent material loss due to combustion due to the incorporation of air (oxygen) and also prevent loss of characteristics of the silk fiber. In addition, it is necessary to design the degree of carbonization (gray to brown) depending on the application.
Set the heating time. In nitrogen gas of 1 to 20 atmospheres, 2
Even when heated at less than 30 ° C., decomposition of the silk protein is slow, carbonization does not proceed, and it cannot be crushed into fine powder in the next step. If it exceeds 350 ° C., the destruction of the protein proceeds rapidly, and the silk protein or its denatured product cannot be left. Further, fine particles having a particle diameter of less than 0.1 μm are expensive in terms of production cost, and there is little demand in the field of use. 10
If it is larger than μm, the surface becomes rough when used as a cosmetic or paint, and the expected luster of the silk material cannot be obtained. In addition,
In the obtained carbonized silk powder, pentopyrene, a carcinogenic substance found in other carbides, was not detected as a result of analysis in PPM units.

According to a second aspect of the present invention, there is provided a method for producing a carbonized silk material powder, comprising: placing a silk material in a sealable firing furnace and drying it in a completely dry state; 230 g of inert gas such as nitrogen gas and helium gas.
A step of heating at −350 ° C. for 5 to 60 minutes to perform carbonization, and subsequently cooling to room temperature, and crushing the carbonized product into fine particles having a particle diameter of 0.1 to 10 μm by a pulverizer. And a process. This production method is suitable for preparing the silk carbonized powder of the first aspect.

[0009] The carbonized product of the silk material according to claim 3 is:
The silk material is placed in a sintering furnace that can be sealed and dried in an absolutely dry state. After that, an inert gas such as nitrogen gas or helium gas at 1 to 20 atm is sealed, and at 230 to 460 ° C., It is a carbonized product that retains the characteristics of the silk material obtained by heating and carbonizing for 60 minutes.

[0010] The processed silk material is intended to be used as activated carbon, a black coloring agent, etc., and is carbonized to black while partially retaining the shape and characteristics of the silk material. It is dried in a sintering furnace and the combustion inside is prevented by replacing the air inside it with an inert gas. The temperature and time are designed by experiments according to the target degree of carbonization. This product is used as it is or after being ground and granulated as activated carbon. When used as it is, the shape of the silk material, for example, the shape of a woven fabric or a non-woven fabric is left as it is, and it can be used as an activated carbon mat. Depending on the degree of pulverization, a powder is obtained that retains the characteristic that the silk material has a hollow fiber shape.
Activated carbon with a large adsorption surface can be obtained by molding into a spherical shape. Further, when the carbonized product is finely pulverized, it can be used as a glossy black coloring agent (cosmetics or the like) depending on the degree of carbonization, and its powder can be used as a drug material.

According to a fourth aspect of the present invention, there is provided a method for producing a carbonized silk material, comprising: placing the silk material in a sealable firing furnace and drying the silk material in an absolutely dry state; Of inert gas such as nitrogen gas, helium gas, etc.
Heating at 460 ° C. for 5 to 60 minutes to perform carbonization treatment, and then cooling to room temperature. It is suitable as a method for producing a carbonized product of the silk material according to the third aspect.

[0012] The carbonized powder according to claim 5 is obtained by placing a silk material in a sealable baking furnace and drying it in an absolutely dry state, and then inert gas such as nitrogen gas or helium gas of less than 1 atm. , And carbonized by heating at 230 to 350 ° C. for 5 to 60 minutes, followed by crushing with a crusher to obtain a fine particle powder having a particle size of 0.1 to 10 μm,
Retains the properties of silk protein. By reducing the pressure of the inert gas, it is effective to set conditions for promoting decomposition even at a low temperature to produce carbide with a low degree of carbonization (carbide close to gray).

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a carbonized powder of a silk material and a method for producing the same according to the present invention will be described below. First, as described above, the silk material which is the starting material of the present invention is selected cocoons, scraps from the silk threading process and the weaving process, cut cocoons, cotton, silk noil, wraps, slivers, or silk fabrics and silk knits. Of used silk products, used silk products, silk thread and silk non-woven fabric, etc., which are inexpensive because China is the main producing country and has not been used effectively.

[0014] The above silk material does not need to be subjected to any special pretreatment. However, when it is desired to obtain a higher purity carbonized carbonized powder, it is subjected to a scouring treatment of a degree of main kneading by a known method and mixed. It is desirable to remove impurities, altered portions, and the like that may be present. When fine particles of about 1 μm are to be obtained, if the silk material is finely cut, cut or pulverized, the carbonization becomes uniform and the pulverization time after firing is reduced.

A firing furnace (called a firing furnace) used for the carbonization treatment includes a chamber in which a heating means and a cooling means are attached to at least one of a lower part and a periphery. The chamber can be ventilated and pressurized and depressurized by being connected to a separately prepared gas supply means (for example, a nitrogen cylinder) and an exhaust means (vacuum pump), and can be processed (a silk material or the like). And has an opening with a lid that can be taken out. In this way, the internal temperature, internal pressure, and internal atmosphere of the firing furnace can be adjusted within a predetermined range.

Gray as a material for cosmetics, drugs, paints, etc.
In a firing procedure for obtaining a reddish brown carbonized powder, a predetermined amount of silk material is placed in a firing furnace. Chamber temperature 10
After the temperature is raised to 0 to 150 ° C., the air and the like in the firing furnace are removed to make the silk material completely dry. An inert gas (usually nitrogen gas) is introduced into the chamber and maintained at a predetermined pressure. The chamber is heated to a predetermined temperature. After a lapse of a predetermined time, the chamber is cooled to room temperature, and the carbonized product is taken out. If necessary, the carbonized product is pulverized by a fine pulverizer. As a pulverizer, for example, a micro jet pulverizer type MJ-7-4U manufactured by Hosokawa Micron Corporation,
A classifier type super separator MSS is preferably used. Similarly, a black carbonized material (referred to as a black processed material) used for a black paint, activated carbon, or the like also has the above processing conditions (temperature,
Time, etc.). In the pulverization, a powder having a particle diameter of less than 0.1 μm can be obtained by using a special pulverizer utilizing fluid energy, but there is a problem that pulverization cost is increased.

[0017]

Embodiment 1 When it is desired to obtain red-based particles of about 5 μm as cosmetic materials, for example, if cutting waste of silk knitting is used as a silk material, the cutting waste has already been scoured, so the refining process is performed. Is not required, and sorting is not required according to the color of the silk material. Approximately 100 g of a silk material from which impurities other than dust and silk have been removed is crushed into a size of about 1 mm by a crusher and placed in a firing furnace (chamber volume: about 0.6 liter). About 1
It is circulated for 0 minutes to remove water and to make it completely dry. After removing the water, the atmosphere in the firing furnace was replaced with nitrogen gas at 5 atm, the temperature was set at 300 ° C., and firing was performed for 10 minutes.
The silk material is partially carbonized and processed into a red gun. It is further cooled to room temperature and taken out of the firing furnace. This was finely pulverized by the above-mentioned microjet pulverizer, and fine particles of a red gun of about 5 μm could be taken out. It can be used as cosmetic material and paint material.

[0018]

Example 2 In the example of Example 1, by heating at 250 ° C. for 10 minutes in a 1-atmosphere atmosphere of nitrogen gas,
Beige fine particles were obtained. Used as a cosmetic material for various foundations.

[0019]

Embodiment 3 The following procedure is used to obtain a black-processed product.
100 g of the cut cocoon from which impurities were removed as a silk material was crushed into a size of about 1 mm by a crusher and stored in a firing furnace (chamber volume: about 0.6 liter).
A hot air at 50 ° C. is circulated for about 10 minutes to remove water and to make it completely dry. After removing the water, the atmosphere in the firing furnace was replaced with nitrogen gas, set to 1 atm, and heated to 350 ° C.
After maintaining for 10 minutes, cool to room temperature and remove. When the carbonized product was confirmed with a magnifying glass, the shape of the silk fiber was left as it was and carbonized. It can be effectively used as activated carbon as it is, but it can be used as a powder for cosmetics (eg, mascara, eyeshadow, eyeline, etc.), black paint by turning it into black powder of about 1 μm using the above-mentioned micro-jet pulverizer. , Was able to obtain the ingredients for medicines.

[0020]

Example 4 In the example of Example 2, gray fine particles were obtained by heating at 200 ° C. for 10 minutes in a 0.5 atm atmosphere of nitrogen gas and then finely pulverizing. A large amount of uncarbonized silk protein remains, and is used as an extraction material for cosmetics or pharmaceutical raw materials for various foundations. I thought.

[0021]

As is apparent from the above description,
The carbonized powder of the silk material of the present invention and a method for producing the same,
The following effects are obtained.

The carbonized powder of the silk material according to claim 1 is obtained by carbonizing a part of the silk protein, coloring it to a predetermined color and pulverizing it, and is used as a raw material for pharmaceuticals or as an additive for cosmetics, paints and the like. It is utilized as. Pharmaceutical raw materials include alanine contained in silk material (effective for improving liver function), gelicin, and serine (effective for lowering blood cholesterol level)
Alternatively, it is used to extract tyrosine (effective for preventing dementia). Since it is finely pulverized, it is efficiently extracted.
Also, carbonized powder that has been carbonized to a hue ranging from gray to reddish brown, when used for coloring cosmetics, paints, foods, etc., should produce a new color tone that exhibits a slight burl-like luster and luster when exposed to light. Becomes possible. Further, it is possible to produce paint having pile fungi.

The method for producing a carbonized powder according to the second aspect is a procedure for efficiently producing the carbonized silk powder according to the first aspect.

The carbonized powder according to claim 3 is completely carbonized while leaving the structural characteristics of the silk fiber,
It has a large function as an activated carbon material, and when using silk woven cloth, non-woven cloth or the like as a raw material, its three-dimensional structure can be used as it is. The pulverized material is used as activated carbon material for beer filtration, water purification, treatment of cleaning waste liquid, etc. by being formed into granules.

The method for producing a carbonized product according to the fourth aspect discloses a procedure suitable for producing the carbonized silk product according to the third aspect.

The carbonized powder according to the fifth aspect is effective as a pharmaceutical raw material because the degree of carbonization of the silk material is small and a large amount of alanine and the like remain.

Claims (5)

[Claims] 1. A silk material is placed in a sintering furnace capable of being sealed and dried in an absolutely dry state. Then, an inert gas such as nitrogen gas or helium gas at 1 to 20 atm is sealed, and 230 to 350 At a temperature of 5 ° C. for 5 to 60 minutes to perform a carbonization treatment, then cooled to room temperature, and then crushed by a crusher so that the particle diameter becomes 0.1 to 10 μm. A carbonized powder of a silk material, wherein the properties of the silk protein are retained. 2. A step of placing the silk material in a baking furnace capable of being sealed and drying it in a completely dry state, and filling the baking furnace with an inert gas such as nitrogen gas or helium gas at 1 to 20 atm. At 230-350 ° C, 5
Heating for 60 minutes to perform a carbonization treatment, and subsequently cooling to room temperature, and a particle diameter of the carbonized treatment product is 0.1 to 10 μm by a pulverizer.
And pulverizing the fine particles into fine particle powders. 3. The silk material is placed in a sintering furnace capable of being closed and dried in an absolutely dry state. Then, an inert gas such as nitrogen gas or helium gas at 1 to 20 atm is sealed, and 230 to 460 is filled. A carbonized product obtained by heating at a temperature of 5 ° C. for 5 to 60 minutes and performing a carbonizing treatment, wherein the characteristics of the silk material remain. 4. A step of placing the silk material in a baking furnace capable of being closed and drying it in an absolutely dry state, and filling the baking furnace with an inert gas such as nitrogen gas or helium gas at 1 to 20 atm. At 230-460 ° C, 5
Heating the carbonized product for 60 minutes, and then cooling it to room temperature. 5. The silk material is placed in a sintering furnace capable of being sealed and dried in a completely dry state, and then inert gas such as nitrogen gas, helium gas or the like is sealed under reduced pressure (less than 1 atm). A fine powder obtained by heating at −350 ° C. for 5 to 60 minutes to perform a carbonization treatment, and then crushing the powder with a crusher so that the particle diameter becomes 0.1 to 10 μm; A carbonized powder of a silk material, characterized by remaining characteristics of: