DE69821916T2 - MODIFIED SILK MATERIALS AND PRODUCTION PROCESS - Google Patents

Description

technological Area

The The present invention relates to a multi-use denatured Silk material obtained by heat treating silk in a gas flow becomes.

The Silk material of the present invention can be used for the purpose of a raw material an outer skin covering product for human use, such as external skin preparations, non-medical Skin products and beauty products or as a medical material, for the purpose of a plant growth promoter or for other purposes, such as an absorbent, a filter material and an abrasive material can be used.

Background Technology

On Raw material from external skin covering products, such as an eyebrow pencil and a hair dye became conventional by heat treatment of organic materials and in particular through incomplete Burning petroleum materials.

carbonized Materials obtained by heat treatment of plants are used as an absorbent and a filter material.

however those materials tend to be due to incomplete combustion of petroleum are made to contain carcinogenic substances develop or thereby during their heat treatment to be contaminated and are therefore Example banned in the United States for use.

On Example of such a material is different from petroleum products in JP-A No. 8-59,219, in the heat treatment silk undergoes to produce a carbonized product that as an outer skin coating product or a filter material is usable.

The The above-mentioned heat treatment of silk is carried out in an inert gas atmosphere Temperature from 600 to 2,000 ° C carried out.

The Heat treatment temperature of 600 ° C is selected to to achieve carbonization.

at the heat temperature treatment below 600 ° C would become a carcinogenic substance (such as benzopyrene) are formed while silk as a raw material due to wax, etc. contained therein to one condition changed by tar becomes what a carbonized product provides without a result of fine particles or granular Products for the practical use are sufficiently usable.

It it is also described that the Heat treatment temperature up to 2,000 ° C from the industrial point of view Cost performance is limited, so not energy consumption at higher Increase temperatures. According to the conventional However, the raw material is invented excessively by the heat treatment carbonized so that a Range of application thereof is limited to one extreme.

Tsukada et al. compare in "Structural Changes of Silk Fibers Induced by Heat Treatment ", Journal of Applied Polymer Science 46 (1992) December 15, pages 1945-1953, the physical properties of silk from two different species, Bombix mori (breeding) and Antheraea pernyi (wild). The investigation was also undertaken about the fine structure changes to investigate on different types of silk fibers, d. H. the molecular conformation, crystallinity and molecular orientation, either in the amorphous or crystalline regions as a function the heat treatment. Furthermore, the modification of the silk fiber structure through thermomechanical analysis, dynamic mechanical measurements, X-ray diffraction analysis and refractive index measurements were examined.

The present invention is in the technological as described above Background reached.

As a result, is an object of the present invention, an application of carbonized silk using improved properties expand it.

A Another object of the present invention is an incompletely carbonized To provide product (or denatured silk) that is suitable for various Purpose is useful due to its inherent and carbonized properties of it, by taking heat treatment from silk as a raw material mild conditions so as to control an amount of carbonization.

Yet another object of the present invention is an industrial Practical process for the production of a denatured silk material by controlling the cost of energy consumption due to the Heat treatment available to deliver.

description the invention

As a result of the inventors' experiments on conditions of silk heat treatment was found, the existence Extent of Carbonization of a raw silk material to be heat treated can be controlled differently while the cost of energy consumption due to the heat treatment can be reduced sufficiently to to carry out the present processes industrially.

The present invention is based on the above information reached and, as will be described below, sets Process for the production of a denatured silk material by Heat treatment of silk under a specific condition, and a denatured silk material that is used as an external skin covering product for the human body, a medical material, a plant growth promoter, an absorbent Material, a filter material and an abrasive material are used will be available.

It namely according to the present Invention (1) a method for producing a denatured Silk material of various colors by heat treatment of naturally Silk, semi-degummed silk or degummed silk or one Mixture of them in one atmosphere of air raft under 0.5 to 1.0 atmospheres at a temperature of 150 to 500 ° C for a certain period of time to disposal posed.

It also (2) is a process for producing a denatured Silk material as described in the above item (1) to disposal with a heat treatment time period in one area from 0.3 minutes to 20 hours.

It is also (3) a method of producing a denatured Silk material of various colors by heat treatment of naturally Silk, semi-degummed silk or degummed silk or one Mixture of them in one atmosphere of inert gas flow, independently selected from each other Nitrogen, helium, neon, argon, krypton and xenon or a mixture thereof and 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time to disposal posed.

It is also (4) a method of producing a denatured Silk material as described in the above item (3) to disposal with the heat treatment time in one area from 0.3 minutes to 20 hours.

It is also (5) a method for producing a denatured Silk material as described in one of the above points (1) or (4) available posed, the natural Silk, semi-degummed silk, degummed silk or a mixture of which in the form of a film, powder, fiber, yarn, fabric, braid or a mixture thereof.

It is also (6) a method of producing a denatured Silk material as described in one of the above points (3) or (4) available the different colors black, yellow, brown, dark brown, Red, violet, blue and gray or natural shades of it lock in.

It (7) will also be a denatured silk material of various types Colors, through heat treatment of natural silk, semi-degummed Silk or degummed silk or a mixture thereof in an atmosphere of air flow underneath 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time to disposal posed.

It (8) also becomes a denatured silk material as in the above Point (7) is available with the heat treatment time in one area from 0.3 minutes to 20 hours.

It (9) also becomes a denatured silk material of various Color, semi-degummed by heat treatment of natural silk Silk, degummed silk or a mixture thereof in an atmosphere of inert gas flow independently selected from each other from nitrogen, helium, neon, argon, krypton, xenon or a mixture of which under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time to disposal posed.

It (10) also becomes a denatured silk material as in the above described point (9) provided, the heat treatment time period is in the range of 0.3 minutes to 20 hours.

It (11) a denatured silk material is also made available, described in one of the above points (7) to (10) The material is used as an outer skin-covering product for the human use is used.

It (12) also becomes a denatured silk material as described provided in the above point (11), the outer skin-covering Product for human use a medical material for the outer skin, a non-medical Material for the outer skin or beauty products is.

It (13) also becomes a denatured silk material as described provided in one of the above points (7) to (10), the denatured silk material being used as a medical Material is used.

It also (14) becomes a denatured silk material as described provided in one of the above points (7) to (10), the denatured silk material for the purpose of being a plant growth promoter is used.

It (15) also becomes a denatured silk material as described provided in one of the above points (7) to (10), the denatured silk material for the purpose of being an absorbent Means or a filter material is used.

It (16) also becomes a denatured silk material as described provided in one of the above points (7) to (10), the denatured silk material for purpose as an abrasive material is used.

On Starting material from denatured silk material of the present Invention closes natural Silk, semi-degummed silk, degummed silk or a mixture of it.

The Silk material lies in the form of a powder, fiber, yarn (like for example knotted Goods, woven and non-woven fabrics), braided material or a mixture thereof.

As a rule, silk is a generic expression, the cocoon yarn, raw silk and includes silk thread and, for example Cocoon yarn protein that is about Contains 28% sericin, wrapped around the fibroin.

The Expression "degummed Silk "like here used mean those materials with hot water have been treated with soap, surfactants such as Example an enzyme activator or alkaline substances such as Example contains sodium carbonate, sodium silicate, etc. (so-called "alkaline degumming") with treated with warm water containing enzymes, such as chemotrypsin, Alkalase, papain, etc. (so-called "enzyme degumming") and treated biologically by microorganisms were (so-called "biological Degumming "), to remove sericin together with wax and inorganic substances.

The Term "natural silk" as used here means those materials that are not degummed.

The Expression "half-degummed Silk "means Intermediates between degummed and natural silk, generally contain less than 15% of sericin.

According to the present invention, such heat treatment is at a temperature in the range from 150 to 500 ° C.

The the reason for this is that silk at a temperature of more than 500 ° C within several minutes in the case of air flow treatment Completely charred or burned while an extent Carbonization is difficult to control when silk is in one inert gas flow, such as nitrogen, helium, etc. is treated.

Farther it takes an impractically long period of time to silk at a temperature of less than 150 ° C to carbonize either in the air or in the inert gas flow.

There the heat treatment of the present invention relative to such one low temperature range, the cost of energy consumption with big industrial advantage can be reduced.

In addition, since the heat treatment of the present invention is in a gas flow under 0.5 to 1.5 atmospheres (an atm. = 1,013 Hp) will become fleeting Components caused by the heat decomposition of the silk are removed from the reaction system by the gas flow, without tar-like Form products as described in JP-A 8-59,219.

The means the heat treatment can be done without residual impurities be carried out in a denatured silk material.

As as a result, the denatured silk material thus treated is dry enough to easily produce fine particles or granular products.

The Starting silk material can be stable and effective in the area of the atmospheres described above be heated.

The denatured silk materials of fine particle or granular form become easily by mechanically grinding the raw silk material obtained in the form of a film or fabric because of the tensile strength of which was extremely reduced by the heat treatment.

The denatured silk material of the present invention changes its Colors, starting from white to Maßgelb, yellow, brown, olive brown, blue, violet, brown-black and last too black, in an order that depends on a degree of heat treatment depends. Accordingly, the denatured silk material is in a powdery state, for example as a base material of products covering the outer skin for the human use, such as a foundation cream, an eyebrow pencil, hair dye, Cheek blush, manicure, Lipstick, eye shadow, etc.

In In this case, the heat treatment can be stopped quickly if a desired one Color occurs, which differentiates the denatured silk material Colors available provides.

This is because that the Heat treatment easily at a temperature of 500 ° C or less in the heating atmosphere can be ended.

The denatured silk material thus produced increases in dependence a lot of non-carbonized (silk) residue different Colors that vary due to the extent of carbonization, and also partially one for Silk has intrinsic biocompatible function.

Therefore shows the denatured silk material of the present invention positive both properties of carbonized substance and silk yourself what is possible makes an application of it for to expand various purposes.

To the Example, the present silk material can not only for the purposes as a medical material and outer skin coating products for the human use that are in direct contact with the skin, used, but also for the purposes as a plant growth promoter, absorbent, Filter material, abrasive material, etc.

The Usability for this purpose is from the later Examples 6 to 11 described.

How As described above, the starting silk material of the present can Invention in the form of a film, powder, fiber, yarn, fabric (such as for example knotted Goods, woven and non-woven fabrics), wattle or mixture of which are available.

If the raw material in the original form after the heat treatment the denatured silk material can be used become as it is.

To the Example when starting silk fabrics (such as knitted goods, woven or non-woven fabric) is heat treated thus shaped product relatively as a material of improved absorbent Properties useful because such a product due to the characteristic three-dimensional twisted structure of fabric fibers has a larger surface area per unit volume.

On on the other hand, the denatured silk material of the present Invention are mechanically ground to form a powder which is a particle size of 0.01 up to 10 microns.

The denatured silk material that has a particle size of less than 0.01 micron has, is expensive to manufacture and also not necessary for the practical use fine.

particle of 10 microns or more are generally due to larger particle size difficult to aggregate, so that denatured silk material is not sufficiently as expected adapts to the skin or tend to appear an incompatibility with skin for certain purposes for which it should be used.

If the denatured silk material of the present invention as one Filter material is used, however the preferred particle size is 0.01 up to 20 mm.

According to the present Invention is provided a denatured silk material that for different purposes due to both inherent and carbonized Properties thereof by heat treatment of silk as a raw material under a mild condition, i.e. H. in a gas flow from 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C so the extent of carbonization to control is useful.

Farther, although a condition of relatively low temperature in the present Invention is used allows the heat treatment in a gas flow under 0.5 to 1.5 atmospheres the heat decomposition of the silk caused volatile components from the To remove reaction system through the gas flow without conventional Tar-like To form products.

Farther, as such, the heat treatment of the present invention in a relatively low temperature range, can the cost of energy consumption can be reduced, creating a Process of manufacture with great industrial advantage disposal is provided.

Best kind to carry out the invention

The present invention is further illustrated by the following examples described in more detail, however, these examples are not meant to be so interpreted to limit the range and variations can be made without departing from the spirit and scope of the present invention to remove.

To the Example can waste silk products as the raw material be used.

example 1

Manufacture of denatured Silk material of different colors

Five grams of crystalline silk powder (similar as described in Japanese Patent No. 2,615,440) were placed in a horizontal glass tube charged, which are then placed horizontally in an electric furnace [available from Shinyo Rikagaku Kizai Co., Ltd. when model KP-7] was placed, around the crystalline silk powder of heat treatment by heating from room temperature at a heating rate of 10 ° C / min. to undergo while nitrogen gas from one end of the glass tube flowed to the other, so as to maintain a gas pressure of 1 ± 0.1 atmospheres.

The color change the crystalline silk in the heating process was visually observed.

A similar Process was carried out using argon gas, and visual observation was done in the same manner as described above repeated.

On The result thus obtained is shown in the attached Table 1.

Table 1

No Difference in color was between nitrogen and argon within observed at a substantial temperature, except that the Color changed to slightly red in the range of 240 to 280 ° C in the argon atmosphere.

Example 2

Manufacture of dark brown 5 micron particles

floss was in a 0.1% aqueous solution of Sodium carbonate, soaked in a bath ratio of 1:50, in it for boiled for one hour, followed by further boiling in replaced aqueous sodium carbonate for one another hour, washed with water and dried to silk yarn to yield (fibroin fiber).

If the degummed silk yarn is then heated using it the device in Example 1 was burned, d. H. in the electrical Oven at 280 ° C in an argon atmosphere at a gas pressure of approximately 0.5 atmospheres for 3 minutes, the silk yarn was partially carbonized to a reddish dark brown to produce burned product or denatured silk material, which partially showed properties of silk protein.

The silk material thus denatured was processed by a microjet grinder [available from Hosokawa Micron Co., Ltd.], followed by classification to give particles having particle sizes of approximately 5 microns.

Example 3

Manufacture of tissue-like denatured silk material

Five grams Silk fabrics were loaded into a horizontal glass tube, which then placed horizontally in an electric oven [available from Shinyo Rikagaku Kizai Co., Ltd. as model KP-7] to the silk fabric a heat treatment by heating from room temperature at a heating rate of 10 ° C / min. to undergo while air flowed from one end of the glass tube to the other, so a gas pressure of 1 ± 0.1 atmospheres to keep.

The color change of the silk fabric in the heating process was observed visually.

The Results obtained were shown in the attached Tables 2-4.

Table 2 Under an air flow from an atmosphere at a predetermined temperature of 170 ° C

Table 3 Under an air flow from an atmosphere at a predetermined temperature of 250 ° C

Table 4 Under an air flow from an atmosphere at a predetermined temperature of 320 ° C

The so heat-treated silk fabrics, especially those materials which were brown or darker in color than reddish-dark brown, can can be easily ground mechanically, for example using a microjet grinder, to colored To yield silk powder.

Example 4

Variation in pressure

Around denatured silk materials under a different combustion condition to surrender was a similar one Experiment on a similar Performed as described in Example 1, except that the pressure of 1.6 atmospheres applied has been.

Farther Example 1 was repeated under a condition of 0.4 atmospheres. As a result, it was found that a stable temperature rise of the crystalline silk powder in the glass tube cannot be achieved can.

Example 5

Manufacture of purple and blue powder

Yamamai silk yarn was in an aqueous 0.1% sodium carbonate solution with a bath relationship from 50 for soaked for one hour, washed with water and dried to degummed silk yarn as a material to be heat treated supposed to surrender.

The thus gummed silk yarn was in an atmosphere of 240 ° C (burn time for 10 minutes) burned by the same device used in [Example 1], around a mainly violet and blue colored Mixture of denatured silk material as a burned product to surrender.

Example 6

Application as an outer skin-covering product

Whites (at Treatment temperature of 25 ° C), pale yellow (at a treatment temperature of 220 ° C) and black-brown (at a Treatment temperature of 300 ° C) denatured silk materials by the heat treatment of [Example 1] were obtained with a beauty product mixed for skin care to produce four test samples A, B, C and D, which comprised various components as follows.

About 0.05 g of these samples A through D were on hypersensitive back skin (from allergic subjects) in an area of 3 cm × 3 cm for 24 hours (as an open batch test).

in the Result caused Sample A as a control after its application a slight itching.

On on the other hand, samples B, C and D made the applied skin smoother than that of an unused part without itching to cause.

• A: ein allgemeines Schönheitsmittelprodukt (das Talkum, Kaolin und Zinkoxid als eine Hauptkomponente enthielt).
• B: 100% des (weißen) Seidenmaterials.
• C: 50% der Kontrollprobe A und 50% des (blaßgelben) denaturierten Seidenmaterials.
• D: 50% der Kontrollprobe und 50% des (schwarzbraunen) denaturierten Seidenmaterials.

In the case of sample B in particular, the skin was comfortably moist and relatively soft with no itching.

• A: a general beauty product (containing talc, kaolin and zinc oxide as a main component).
• B: 100% of the (white) silk material.
• C: 50% of control sample A and 50% of the (pale yellow) denatured silk material.
• D: 50% of the control sample and 50% of the (black-brown) denatured silk material.

Example 7

Application as a plant growth promoter

ten Grams of brown denatured silk material, which by heat treatment obtained from [Example 1] (at a treatment temperature of 260 ° C) was added to 1,000 g of water.

The Mixture of denatured silk material and water thus prepared (in an amount of 100 g) was once a week on Madagascan seeds Evergreen, the one in a planter of about 20 cm wide, approximately 60 cm length and roughly 15 cm high was planted, applied.

To Two months ago a plant growth-promoting effect of the denatured Silk material observed.

A treated group of Madagascan evergreens (in bundles of 10 plants) and an untreated control group of Madagascan evergreens (in Bundle up of 10 plants) were cut off above the bottom and weighed. It was found that the Weight of the untreated bundle of Madagascan evergreens Was 110 g while that of the treated bundle of Madagascan evergreens 150 g was.

Example 8

Application as an absorbent medium

Two Grams of dark brown silk powder, as by the heat treatment obtained from [Example 3] (see Table 4) were in a cotton bag filled, the for five hours in a liter of slightly cloudy Fresh water (collected from Lake Biwa) was kept. As a As a result, the transparency of the water was improved, with little Turbidity.

Example 9

Application as an odor absorbing Medium (deodorant)

A whole body of rotten fish (300 g weight) was left in a sealed chamber of about 6 m ³ for one hour, and after the fish was taken out of the chamber, 100 g of the dark brown crystalline silk powder was obtained as by the heat treatment of [Example 3] (see Table 4) used to be left in it.

To The smell of the rotted fish was relative to you for 6 hours low levels decreased.

Example 10

Application as an abrasive material

The white (at a treatment temperature of 100 ° C) and brown (at a treatment temperature of 270 ° C) the heat treatment of crystalline silk powder obtained [Example 1] have been used as an abrasive material.

Glass and metal (copper) plates as test specimens were thoroughly wiped with an alcohol-containing glass polishing cloth and an abrasion method by soaking the white silk powder on the surface of each specimen in an amount of 2 g / 50 cm ² and polishing with a dry glass polishing cloth and then subjected to a plastic board under pressure of 10 kg / cm ² for one hour.

Farther the glass and metal surfaces were thoroughly mixed with the alcohol-containing Polished glass polishing cloth. As a result of visual observation of the glass and metal surfaces by a reflection test it was found that the brilliance of the samples were improved due to the abrasion process.

The reddish-brown crystalline silk powder obtained by the heat treatment of [example 3] (see Table 3) was obtained for an abrasion test on a similar one Way used as described above.

As a result of visual observation of the glass and metal surfaces A reflection test was found to determine the brilliance of the samples improved to a slightly greater extent than the white one crystalline silk powder.

Example 11

Application as a filter (a filter material)

The by the heat treatment of Example 1 at a treatment temperature from 100 ° C (see Table 1) obtained white Crystalline silk powder was used as a filter material for the test.

The white silk powder was put between two flat boards and compressed under pressure of 20 kg / cm ² for hardening, thereby obtaining a powder board of 2 mm in thickness.

The Powder board was placed between filter paper to make a filter material to build. Water collected from Lake Biwa was under 0.5 atmospheres Absorbent using the filter material so produced filtered, giving a water of considerably improved turbidity has been.

The obtained by the heat treatment of [Example 3] (see Table 3) reddish-brown crystalline silk powder was prepared in a similar manner to that described above for one Filter test used.

As a result was found that showed the turbidity of the filtrate in one Extent of less than that of the white one crystalline silk powder was significantly improved.

industrial applicability

The Silk material of the present invention can be used as one for the purpose Raw material for an outer skin coating product for the human use, such as external skin preparations, non-medical Skin products and beauty products or used as a medical material for the purpose as a plant growth promoter or for other purposes such as an absorbent, a filter material and an abrasive Material. Furthermore, the silk material can very well be used as a coating for materials, coloring of clothing.

Claims (16)

Process for producing a denatured silk material of various colors, characterized in that it involves the heat treatment of natural silk, semi-degummed silk or degummed side or a mixture thereof in an atmosphere of air flow below 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time. A method according to claim 1, characterized in that a Heat-treatment period is in the range of 0.3 minutes to 20 hours. Process for the production of a denatured silk material of different colors, characterized in that there is a Heat treatment from more natural Silk, semi-degummed silk or degummed silk or one Mixture of them in one atmosphere of inert gas flow, independently selected from each other from nitrogen, helium, neon, argon, krypton and xenon or one Mixture thereof under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for one includes a certain period of time. A method according to claim 3, characterized in that the Heat-treatment period is in the range of 0.3 minutes to 20 minutes. Method according to one of claims 1 to 4, characterized in that that the natural Silk, semi-degummed silk, degummed silk or a mixture of which in the form of a film, powder, fiber, yarn, fabric, braid or a mixture thereof. A method according to claim 3 or 4, characterized in that different Colors black, yellow, brown, dark brown, red, violet, blue and Gray or natural colors include of it. Denatured silk material of various colors, characterized in that it by heat treatment of natural Silk, semi-degummed silk or degummed silk or one Mixture of them in one atmosphere of air flow under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time was obtained. Denatured silk material according to claim 7, characterized characterized that the Heat treatment time in the range of 0.3 minutes to 20 hours lies. Denatured silk material of various colors, characterized in that it by heat treatment of natural Silk, semi-degummed silk, degummed silk or a mixture of it in an atmosphere of inert gas flow, independently selected from each other from nitrogen, helium, neon, argon, krypton, xenon or a mixture of which under 0.5 to 1.5 atmospheres at a temperature of 150 to 500 ° C for a certain period of time was obtained. Denatured silk material according to claim 9, characterized characterized that the Heat treatment time in the range of 0.3 minutes to 20 hours lies. Denatured silk material according to one of claims 7 to 10, characterized in that the material for the purpose of being an outer skin coating product is used for human use. Denatured silk material according to claim 11, characterized characterized in that the outer skin coating product for the human use a medical material for the outer skin, non medical material for the outer skin or beauty product is. Denatured silk material according to one of claims 7 to 10, characterized in that the denatured Silk material used for the purpose as a medical material becomes. Denatured silk material according to one of claims 7 to 10, characterized in that the denatured Silk material used for the purpose as a plant growth promoter becomes. Denatured silk material according to one of claims 7 to 10, characterized in that the denatured Silk material for the purpose of being an absorbent or a filter material is used. Denatured silk material according to one of claims 7 to 10, characterized in that the denatured Silk material is used for the purpose as an abrasive material.