KR100393831B1 - Modified silk materials and process for the production thereof - Google Patents

Abstract

The present invention further extends the field of adaptation that utilizes the carbide properties of the silk, and heats the silk under calm conditions and adjusts the degree of carbonization to various applications having both the properties of the carbide and the sample of the silk. It is aimed at obtaining useful incomplete carbides (i.e. modified dog materials) and obtaining industrially feasible methods for producing modified dog materials by suppressing the energy consumed by heat treatment at low cost.

The present invention is to heat the unrefined silk, semi-refined silk, refined silk, or a combination thereof in a certain period of time under an atmosphere of a gas pressure of 0.5 ~ 1.5 atm, air temperature 150 ~ 500 ℃ A modified dog material having various colors can be obtained.

Description

Modified dog material, manufacturing method {MODIFIED SILK MATERIALS AND PROCESS FOR THE PRODUCTION THEREOF}

BACKGROUND ART Conventionally, there is a material obtained by incomplete combustion of a petroleum-based material, which is used as a coating material for human skin such as eyebrows, muds, gray hair dyes, etc. by heating an organic material.

Moreover, the carbide obtained by heat-processing a plant is used as an adsorption material and a filter medium.

However, a material obtained by incomplete combustion of a petroleum-based material is prohibited from use in the United States, for example, because of the possibility of generating or mixing with carcinogenic substances during the heat treatment.

Regarding combustion materials other than petroleum-based materials, it is already described in Japanese Patent Application Laid-Open No. 8-59219 to use carbide obtained by heat treatment of a silk as a coating material or filter material for human skin.

In this invention, heat treatment of a silk is performed at 600-2,000 degreeC in inert gas atmosphere.

In the above invention, the heating temperature is set at 600 ° C or higher to completely carbonize.

That is, at temperatures below 600 ° C., carcinogenic substances (lenspyrene) may be generated, and in addition, there is a defect in usability since the product (carbide) does not become a particulate or granular form due to wax or the like in a silk material. .

It is said that the upper limit of the heating temperature is 2,000 ° C. because the energy consumption is too high at 2,000 ° C. or higher, making it difficult to use industrially in terms of cost. However, in this conventional invention, the degree of carbonization of the heat-treated one is very large and therefore extremely limited in the application field.

The present invention has been made under such technical background.

That is, this invention aims at further expanding the application field which utilized the carbide characteristic of a dog.

The objective of this invention is to obtain incomplete carbides (ie, modified dog materials) useful for various applications that have both the properties of carbide and sample properties by heat treating the honey under more calm conditions.

In addition, an object of the present invention is to provide a method for producing a modified dog material which can be industrially implemented by suppressing energy consumption by heat treatment at a low cost.

The present invention relates to a modified dog material useful for various applications obtained by heat treating a dog in a gas stream.

The modified dog material of the present invention can be used for application to human skin coats, medical members, plant growth promoters, etc., and also for absorbents, filters, and abrasives, such as outer medicines, outer medicines, or cosmetics.

As a result of various studies on the conditions of heat treatment of the dog, the inventors found that the carbonization degree of the heat treatment product can be adjusted in various ways, and that the energy consumption due to the heat treatment can be suppressed with low cost, thereby being industrially feasible. .

The present invention has been accomplished on the basis of this finding, and a method for producing a modified dog material obtained by heating a dog such as the following indication under specific conditions, a coating material for human skin, a medical member, a plant growth promoter, an adsorbent, a filter medium, and It is to provide a modified dog material suitable for applications such as abrasives.

In other words, the present invention (1) the unrefined, semi-refined, refined, or a combination of them for a certain period of time under an atmosphere of air pressure of 0,5 to 1.5 atm, air temperature 150 to 500 ℃ It is a manufacturing method of modified dog material which obtains modified dog material which has various colors by heat processing.

And (2) The heat treatment time is in the method of producing the modified dog material according to the above (1), which is in the range of several minutes to 20 hours.

And (3) unrefined, semi-refined, refined, or a combination of them by inert gas selected from nitrogen, helium, neon, argon, krypton and xenon alone or a mixture of these gases. The present invention relates to a method for producing a modified dog material obtained by heat treatment for a certain period of time under an atmosphere of a gas pressure of 0.5 to 1.5 atm and a temperature of 150 to 500 ° C.

And (4) heat processing time is in the manufacturing method of the modified dog material of said (3) which is a range of several to 20 hours.

And (5) the above (1), wherein the unrefined, semi-refined, refined or composites thereof are in the form of films, powders, fibers, yarns, fabrics, compositions or composites thereof. The method of manufacturing a modified dog material according to any one of (4).

And (6) a method for producing a modified dog material according to any one of (3) or (4), wherein the various colors are black, yellow, dark, brown, violet, blue, or gray colors or their intermediate colors. .

And (7) obtained by heating the unrefined, semi-refined, refined, or mixtures thereof for a certain period of time under an atmosphere of air pressure of 0.5 to 1.5 atm and a temperature of 150 to 500 ° C. It is in modified dog material with various colors.

And (8) heat processing time is in the modified dog material of said (7) which is a range of several to 20 hours.

And (9) the gas pressure of unrefined, semi-refined, refined, or mixtures thereof, inert gas selected from nitrogen, helium, neon, argon, krypton and xenon alone or a mixture thereof. It is in a modified dog material with various colors obtained by heat treatment for a certain time in an atmosphere of 0.5 to 1.5 atm and a temperature of 150 to 500 ° C.

And (10) The heat treatment time is in the modified dog material according to the above (9), which ranges from several minutes to 20 hours.

And (11) The modified dog material according to any of the above (7) to (10), wherein the modified dog material is used for the coating material use for the human skin.

In addition, (12) the coating material for human skin is present in the modified dog material according to (11) above, which is composed of an outer shell pharmaceutical part, an outer shell drug or cosmetic.

And (13) The modified dog material according to any of the above (7) to (10), wherein the modified dog material is used for the use of the medical member.

And (14) The modified dog material according to any of the above (7) to (10), wherein the modified dog material is used for plant growth promoting material use.

And (15) The modified dog material according to any of the above (7) to (10), wherein the modified dog material is used for adsorption or filter medium applications.

And (16) The modified dog material according to any one of the above (7) to (10), wherein the modified dog material is used for abrasive use.

The silk material, which is the starting point of the modified dog material of the present invention, is unrefined, semi-refined, refined, or composite thereof.

The silk material may be in the form of powder, fiber, yarn, fabric (knitting fabric, woven fabric, nonwoven fabric, etc.), fabric, or a composite thereof.

In general, silk is a generic term for silk thread, raw silk and silk thread. For example, silk silk is a protein of fibroin (about 70%) and sericin (about 28%). It exists like a fibroin.

Here, the refined product of silk is treated with hot water containing a surfactant such as soap or ragen power, or alkaline substances such as sodium carbonate and sodium silicate (so-called "alkali refining"), chymotrypsin, alkalase , Treated with hot water containing enzymes such as papain (so-called "enzyme refining"), and those incubated with microorganisms (so-called "hatching refining"), and sericin are excluded from wax and minerals.

In addition, unrefined product of a dog refers to the dog which was not refined.

In addition, the semi-refined substance of the silk refers to the intermediate between the unrefined substance and the refined substance, and usually sericin is 15% or less.

In the manufacturing method of this invention, heat processing temperature is performed in 150-500 degreeC.

The reason for this is that in the case of the treatment in the air stream, the carbon is completely carbonized or burned in the moisture at a temperature exceeding 500 ° C, and in the case of the treatment in the inert gas stream such as nitrogen and helium, the degree of carbonization is adjusted. This is difficult to control.

It is also because it is not practical at a temperature below 150 ° C. for a long time of carbonization in air and air stream of inert gas.

Since the manufacturing method of this invention is performed in such a comparatively low temperature range as heat processing, it is very advantageous industrially by suppressing energy consumption by low cost.

In addition, in the manufacturing method of the present invention, since the heat treatment is performed under a gas flow of 0.5 to 1.5 atm (one pressure is 1013 Hp), the volatiles generated by the thermal decomposition of the gas stream are removed to the outside of the system. The sticky tar phase product described in the publication is not generated.

In other words, the heat treatment can be carried out without remaining impurities in the strained material.

Therefore, since the modified dog material produced by heat processing is dried, the modified dog material of a particulate form or a granular form can also be obtained easily.

In the above air pressure range, the raw material can be heated stably and efficiently.

In addition, the raw material silk material having a film-like or cloth-like form can be easily changed into a fine-grained or granular modified dog material by mechanical grinding because the tensile strength is extremely reduced by heat treatment.

Since the modified dog material of the present invention is changed to white, pale yellow, yellow, brown, dark brown, blue, purple, black brown, and then black according to the degree of heat treatment, for example, the powdered powder is foundation, eyebrow paint, gray hair dyeing. It can be used as a coating material for human skin, such as softening paper, nail polish, rouge, and eye shadow.

In this case, the heat treatment can be quickly terminated in the desired color step to obtain a modified dog material of various colors of interest.

This is because the heating stop can be easily performed at an ambient temperature of 500 ° C. or lower.

The modified dog material thus obtained has various colors depending on the size of the uncarburized portion (dog) depending on the degree of carbonization, and also partially has the inherent biocompatibility function.

Therefore, the properties of carbides and properties of the original dogs are actively shared, and the scope of application can be expanded and used for various applications.

For example, it can be used for applications such as plant growth promoting material, absorbent material, filter material and abrasive material, in addition to medical material or human skin coating material which is in direct contact with skin.

Usefulness for these uses will be revealed by later Examples 6-11.

As described above, the form of the silk material used as the raw material of the modified dog material can adopt various forms such as films, powders, fibers, yarns, fabrics (knitting fabrics, woven fabrics, nonwoven fabrics), fabrics and composites thereof.

Therefore, when the form after heat treatment is also maintained in the form of the raw material, it can be used directly in the form.

For example, when the fabric (woven fabric, knitted fabric, nonwoven fabric) is heat treated, the fibers characteristic of the fabric are entangled in three dimensions, so that the surface area per unit volume is large, making it an optimal material as a modified dog material using the adsorption function.

When the modified dog material was mechanically powdered, it was pulverized to 0.01 to 10 microns.

Particles of modified dog material smaller than 0.01 micron are higher in manufacturing cost and further, practically, finer particles are not necessary.

The microparticles of modified dog material larger than 10 microns are also used depending on the object to be used, but due to the large particle size, the cohesiveness is poor, and when applied to the human body, it may not be friendly to the skin more than expected, or the skin may feel uncomfortable.

When the modified dog material is used as the filter medium, the crushed size is preferably 0.01 mm to 20 mm.

Modifications useful for various uses that share the properties as a carbide and the original properties of the dog by adjusting the degree of carbonization by heating the dog under calm conditions (gas pressure of 0.5 to 1.5 atm and air flow at 150 to 500 ° C). A silk material can be obtained.

Moreover, although the manufacturing method of this invention heat-processes under the gas stream of 0.5-1.5 atmospheres of gas pressure although the heat processing conditions of comparatively low temperature are employ | adopted, the volatile component which gas stream produces | generates by thermal decomposition is carried out out of the system. This does not produce a sticky tar product as in the prior art.

In addition, since the heating temperature is relatively low, the energy consumed by the heat treatment can be suppressed at low cost, thereby providing a manufacturing method which is very advantageous in industry.

Best Mode for Carrying Out the Invention

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples, and various modifications can be made without departing from the spirit of the invention.

For example, it is applicable even if it uses waste materials, such as a silk product.

Example 1

Example of obtaining modified dog material with various colors

5 g of crystalline powder (the same as the crystalline powder described in the specification of Patent No. 2615440) is placed in a horizontally placed glass tube, and the glass tube containing the crystalline powder is placed horizontally and an electric furnace (Shinyo Rigaku Kigi ( Note), KP-7) was installed and heated to room temperature at a temperature increase rate of 10 ℃ / min while nitrogen gas was flowed from one end of the glass tube to the other at a gas pressure of 1 ± 0.1 atm.

And, the color change of the crystalline powder in the temperature increase process was visually observed.

The same treatment was also performed with argon gas to observe the color change of the crystalline silk powder during the temperature increase process in the same manner.

These results are shown in Table 1.

Temperature (℃) color Nitrogen gas Argon gas 25 White White 100 White White 150 White White 200 White White 220 buff buff 240 buff Light pink 250 yellow Light pink 260 Brown Skin color 270 Brown Light brown 280 mum Earthy brown 290 Earthy brown Earthy brown 300 Earthy brown Light brown 310 Earth color Earth color 320 black Earth color 330 black Earth color

In addition, argon gas is slightly red in nitrogen gas and argon gas in the range of 240 ° C. to 280 ° C., but the colors are the same in the other temperature ranges.

Example 2

Example of obtaining 5 micron dark brown particles

Raw silk was immersed in a 0.1% aqueous solution of 0.1% sodium carbonate in a bath ratio of 50, and after boiling for 1 hour, the aqueous solution of sodium carbonate was newly regenerated for 1 hour, washed with water and dried to obtain silk yarn (fibroin fiber).

Next, using the apparatus of Example 1, the temperature was 280 DEG C, the firing time was set to 3 minutes, and the air flow condition of about 0.5 atm was set. A reddish brown plastic product (modified dog material) was formed, leaving some of the properties of.

This modified dog material was ground in a microjet mill (manufactured by Hosokawa Micron Co., Ltd.), and classified again to obtain particles of about 5 microns.

Example 3

Example of obtaining modified dog material in woven fabric

5g of silk fabric is placed in the horizontally placed glass tube, and the glass tube is placed horizontally and installed in an electric furnace (Shinyo Rigaku-Kujizai Co., KP-7 type). The silk fabric was heated by heating at room temperature at a temperature increase rate of 10 ° C./min while flowing to atmospheric pressure. And, the color change of the silk during the temperature increase process was visually observed.

The results are shown in Tables 2 to 4.

In air flow of set temperature 170 degrees Celsius 1 atmosphere time 1 to 2 hours 2 to 5 hours 10 to 20 hours Color of silk buff yellow Brown

In air flow of set temperature 250 degrees Celsius 1 atmosphere time 0.3 to 2 minutes 8-20 minutes 0.5 to 1 hour 1.5 to 3 hours 4 to 6 hours More than 7 hours Color of silk buff Brown maroon Purple brown Dark brown black

In air stream of set temperature 320 degrees Celsius 1 atmosphere time 20 to 40 seconds 1-2 minutes 2.5 to 4 minutes 5 to 10 minutes More than 13 minutes Color of silk Brown maroon Light brown Dark brown Earth color

If the coloring is brown or reddish brown or more, the heat treated silk fabric can be easily mechanically pulverized and colored using a microjet mill or the like.

Example 4

Example of changing pressure

The same experiment as in Example 1 was conducted except that the atmospheric pressure was 1.6 atm in order to obtain a modified dog material according to different firing conditions.

The same experiment as in Example 1 was conducted except that the atmospheric pressure was 0.4 atm. In these cases, the temperature of the crystalline silk powder in the glass tube was not increased.

Example 5

Purple, an example of obtaining a blue powder

Cheonjamsa was used as a material of Cheonjamsa obtained by washing with water after drying for 1 hour in a 0.1% aqueous solution of sodium carbonate at a bath ratio of 50 times.

When the fabric was fired using an apparatus of Example 1 in a temperature of 240 ° C. (firing time 10 minutes), a fired product (modified dog material) mixed with violet and blue was produced.

Example 6

Example as coating material for outer skin

The modified dog material of white (treatment temperature 25 ° C), pale yellow (treatment temperature 220 ° C), and black brown (treatment temperature 300 ° C) obtained in the heat treatment of Example 1 was mixed with the skin care cosmetic as follows. , B, C and D were prepared.

Then, about 0.05 g was applied for 24 hours (release patch test) on the skins of sensitive skin (allergic skin) in the size of 3 to 3 cm of A to D (release patch test) to see the results.

In the case of A, the resultant A was slightly skewed after application.

After application of B, C, and D, there was no skew, and it was smoother than the unapplied skin part.

In particular, after the application of B, it was moist and smooth without any itch.

A: general cosmetics (main ingredient talc, kaolin, zinc oxide)

B: 100% of silk material (bag)

C: A 50% + Denatured dog material (pale yellow) 50%

D: A 50% + Denatured Dog Material (Black Brown) 50%

Example 7

Examples of plant growth promoters

10 g of brown (modified dog material) obtained in the heat treatment of Example 1 was treated with 1,000 g of water.

Water (100 g) containing this modified dog material was given weekly to color seedlings planted in a container of width 20 cm, length 60 cm and length 15 cm.

After 2 months the shape was observed.

As a result, when the weights of the surface portions of the color rains (10 bubbles) and the quasi-color rains (10 bubbles) without water were measured, the water color ratio was 150 g with respect to 110 g of the color rain without water.

Example 8

Example as adsorbent

2 g of dark brown crystalline powder obtained in the heat treatment of Example 3 (see Table 4) was placed in a cotton cloth bag, and the bag was placed in 1 liter of fresh water (collected from the lake) for 5 hours. Less haze and better transparency.

Example 9

Example as an adsorbent (deodorant) against odor

After one hour (300 g) of decayed fish was placed in an airtight chamber of about 6 m 3, the fish was taken out outdoors, and then dark brown (see Table 4) crystallinity obtained in the heat treatment of Example 3 above. 100 g of silk powder was allowed to stand indoors.

Six hours later, the odor of the room was very low.

Example 10

Example as abrasive

Polishing was carried out using crystalline silk powder of white (process temperature 100 占 폚) and brown (process temperature 270 占 폚) obtained in the heat treatment of Example 1.

For polishing, put glass and metal (copper) on glass cloth and clean it with alcohol. Then, put 2g of white and brown crystalline powder per 50cm2, and put dry eyeglass cloth and plastic plate on it. The glass and metal surfaces were polished for 1 hour by weighting.

After that, the glass and metal surfaces were cleaned well by feeding alcohol into the eyeglass cloth. The surface was observed by reflecting light onto the glass and metal surfaces, and the gloss was improved by polishing.

In the same manner, red crystalline brown powder (see Table 3) obtained by the heat treatment in Example 3 was ground.

As a result, the surface was observed by reflecting light onto the glass and metal surfaces, and the gloss was improved by polishing, and the degree of gloss was slightly higher than that of the white crystalline silk powder.

Example 11

Example as filter (filter material)

The use experiment as a filter was performed using the crystalline silk powder of the white (process temperature 100 degreeC (refer Table 1)) obtained by the heat processing of Example 1.

Each of these white dog powders was sandwiched between plates, pressurized at a pressure of 20 kg / cm < 2 > to harden to form a plate-like body made of powder having a thickness of 2 mm.

The plate-like body by this powder was sandwiched between filter papers, and it was set as the filter. Subsequently, suction filtration was performed at 0.5 atm using non-encrypted water. The degree of water clouding after filtration was considerably less.

In the same manner, the use experiment as a filter was carried out using crystalline brown powder of reddish brown (see Table 3) obtained in the heat treatment of Example 3.

As a result, the degree of water clouding after filtration was considerably smaller, and the degree of clouding was further smaller than that of the former white crystalline powder filter.

The modified dog material of the present invention is intended for use as a coating material or medical member for human skin of materials such as outer medicines, outer medicines, or cosmetics, as well as for plant growth promoters, and as absorbents, filters, and abrasives. It can be used, but it also has many applications such as material coating and medical dyeing.

Claims (16)

Modified dog material having various colors by heating unrefined, semi-refined, refined products of silk, or composites of them for a certain period of time under an atmosphere of air pressure of 0.5 to 1.5 atm and temperature of 150 to 500 ° C. Method of producing a modified dog material, characterized in that obtaining. The method for producing a modified dog material according to claim 1, wherein the heat treatment time is in a range of several minutes to 20 hours. Unrefined, semi-refined, refined, or a combination of these compounds is prepared by inert gas selected from nitrogen, helium, neon, argon, krypton and xenon alone or a mixture of these gases. A method of producing a modified dog material, characterized by obtaining a modified dog material having various colors by heat treatment for a predetermined time in an atmosphere of air flow of 150 ~ 500 ℃. The method for producing a modified dog material according to claim 3, wherein the heat treatment time is in a range of several minutes to 20 hours. 5. The method of claim 1, wherein the unrefined, semi-refined, refined, or composites thereof are in the form of films, powders, fibers, yarns, fabrics, crudes, or composites thereof. Method for producing a modified dog material, characterized in that. The method for producing a modified dog material according to any one of claims 3 to 4, wherein the various colors are black, yellow, dark, brown, red, violet, blue, or gray-based or intermediate colors thereof. . Unrefined, semi-refined, refined, or composites of the silk have various colors obtained by heating for a certain period of time under an atmosphere of air pressure of 0.5 to 1.5 atm and a temperature of 150 to 500 ° C. Modified dog material made with. 8. The modified dog material according to claim 7, wherein the heat treatment time is in the range of several minutes to 20 hours. Unrefined, semi-refined, refined, or combinations of them are prepared by inert gas selected from nitrogen, helium, neon, argon, krypton, and xenon alone, or gas mixtures of 0.5 to 1.5 atm and gas. Modified dog material, characterized in that it has a variety of colors obtained by heat treatment for a period of time in the atmosphere of 150 ~ 500 ℃ airflow. 10. The modified dog material according to claim 9, wherein the heat treatment time ranges from several minutes to 20 hours. The modified dog material according to any one of claims 7 to 10, wherein the modified dog material is used for a coating material for human skin. The modified dog material according to claim 11, wherein the coating material for human skin is made of an outer skin pharmaceutical part, an outer skin drug or cosmetic. The modified dog material according to any one of claims 7 to 10, wherein the modified dog material is used for the use of a medical member. The modified dog material according to any one of claims 7 to 10, wherein the modified dog material is used for plant growth promoting material use. The modified dog material according to any one of claims 7 to 10, wherein the modified dog material is used for adsorption material or filter medium use. The modified dog material according to any one of claims 7 to 10, wherein the modified dog material is used for an abrasive material.