JP2000027027A - Polymer composite material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a formed material such as yarn, film, sponge, etc., made of a composite comprising silk and cellulose and/or chitin or chitosan and to obtain amino acid polymer composite material such as yarn, film, sponge, etc., having the characteristic functions of these components. SOLUTION: Silk is dissolved in a mixed solution of three components of a halogenated alkali metal salt or alkaline earth metal salt, a lower alcohol and water and salts and the alcohol are removed by dialysis to give 2-20% silk solution. The silk solution, 3-10% cellulose solution by a viscose method and 2-10% solution of chitin or chitosan acylatesd derivative are used as a forming stock solution and spun, made into a film or molded into a sponge to give a polymer composite material such as yarn, film, sponge, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polymer composite solution comprising silk, cellulose, chitin chitosan or an acylated chitin chitosan derivative, and a method for producing a fiber, a film or a sponge by a wet method on an industrial scale. It concerns the manufacturing method. Various characteristics of silk are clothing,
It is very useful in the medical industry. However, since it is more difficult to mold than the solution state of silk itself and the price is high, there is a disadvantage that it cannot be said that it is sufficiently utilized in the above-mentioned industrial fields. (B) silk and rayon, (b) silk and chitin chitosan or an acylated chitin chitosan derivative, (c) a reconstituted product of silk and rayon with chitin chitosan, (d) silk and rayon in the present invention. The composite material of each of the reconstituted product with the chitin-chitosan acylated derivative solves the above-mentioned difficulties caused by silk itself,
Production on an industrial scale has become possible, and industrial use has become fully possible. In addition, the waste silk, which has been handled as industrial waste in the past, can be effectively used.

[0002]

2. Description of the Related Art Conventional silk is used for 1) a concentrated solution of calcium chloride,
2) concentrated solution of lithium bromide, 3) concentrated solution of sodium thiocyanate, 4) concentrated solution of halide of alkali metal or alkaline earth metal, 5) dissolved in Schweitzer solution or the like, or lower alcohol. Attempts have been made to spin, form, and mold the solution to which it has been added. However, spinning, film formation, and molding are significant difficulties in producing industrially effective products. Chitin chitosan or an acylated chitin chitosan derivative is xanthogenized into a viscos solution or simply dissolved in caustic soda solution and mixed with cellulose biscos and spun. It is described in Japanese Patent No. 2736868 and Japanese Patent Application No. 9-54074.

[0003]

It is well known that silk has various physiological activities, and it is also organoleptically excellent. However, although attempts have been made to produce various molded articles by using silk in a solution state, industrial production of molded articles is difficult due to the difficulty of molding and the high cost. In addition, attempts to mold chitin chitosan itself, which has a natural effect derived from natural products like silk, or to integrate chitin chitosan and cellulose, have been conventionally desired, but at present, they are still industrially still available. It is hardly successful. The present invention relates to a method for producing a fiber, a film or a sponge or the like formed from a composite made of silk and cellulose and / or chitin chitosan, and a molding of a fiber, a film or a sponge or the like having a function unique to each component. It is an object of the present invention to provide a polymer composite comprising a body.

[0004]

SUMMARY OF THE INVENTION The present inventor has sought to overcome the difficulty of producing fibers and molded articles from a solution state.
Chitin chitosan or chitin chitosan acylated derivative or a mixture thereof in a solution state and homogenized to form a composite,
As a result of earnest research on the technology of manufacturing molded products such as fibers, films or sponges, and further, the technology of manufacturing viscose cellulosic fibers, films or sponges,
Finally, the present invention has been completed.
Is a mixed solvent of silk and an alkali metal halide or alkaline earth metal salt, a lower alcohol (including the case of 0 content), and three components of water (two components when the alcohol content is 0). And then dialyzed to remove salts and alcohols, or concentrated to a concentration of 2 to 2
A 0% silk solution, a bisco-process cellulose solution having a cellulose concentration of 3 to 10%, a chitin chitosan or chitin chitosan or a chitin chitosan acylated derivative alkaline solution having a chitin chitosan acylated derivative concentration of 2 to 10% And a single solution or a mixed solution thereof is mixed to form a stock solution, and then a stock solution having a silk ratio of 2 to 98% in the solute component is prepared. This is a method for producing a polymer composite comprising a molded article such as a fiber, a film or a sponge by spinning, film-forming and molding by adding a protein denaturation step. The second is a polymer composite made of a molded product such as fiber, film or sponge produced by the first production method. Thirdly, silk is made of an alkali metal halide or an alkaline earth metal salt, a lower alcohol (including a case where the content is 0),
The three components of water (two components when the alcohol content is 0) are dissolved in a mixed solvent and then dialyzed to remove salts and alcohols, or the solution is concentrated or concentrated to a concentration of 2 or less.
A silk solution of about 20% to a cellulose solution having a cellulose concentration of 3 to 10%, a chitin chitosan or a biscosylated chitin chitosan having a chitin chitosan acylated derivative concentration of 2 to 10% or A chitin-chitosan acylated derivative solution and a single solution or a mixed solution thereof are mixed to form a stock solution, and then a stock solution having a silk ratio of 2 to 98% in the solute component is prepared. A method for producing a polymer composite comprising a molded product such as a fiber, a film, or a sponge by spinning, film-forming, and molding by adding a protein denaturation step in the middle as necessary. The fourth
The present invention relates to a polymer composite comprising a molded product such as a fiber, a film or a sponge produced by the third production method.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The ratio of silk in a molded product used in the present invention is 2 to 96%. In this case, the silk used may be scoured into fibroin by a conventional method or may contain sericin, depending on the final purpose, and may be appropriately selected depending on the type of silk in the desired product finally. Good. Alkali metal or alkaline earth metal halide solution used for dissolution, or the dissolution method is also performed by a conventional method,
No alcohol is required. It is well known that severe dissolution conditions can cause depolymerization. When high molecular weight silk is finally required, the desired product can be obtained by adjusting the dissolution temperature and dissolution time. When bistinizing chitin chitosan,
What is necessary is just a thing of the quality which the reaction advances. For details, refer to Japanese Patent No. 2736868, Japanese Patent Application No.
No. 54069. The alkali solution is described in detail in Japanese Patent Application No. 9-74070. Further, chitin chitosan acylated derivatives include, for example,
There is a propionylated chitosan as shown in the formula below.

[0006] Viscosification as in the case of chitin chitosan,
Further, it can be converted into an alkaline solution.

[0007] Chitin chitosan or an acylated derivative thereof is a polymer derived from a natural product, and is well known to have a physiological activity improving function in addition to being a preferable material in consideration of global environment. There are many academic reports on the function of silk, and various functions are recognized in addition to chitin chitosan, which is a polymer derived from natural products.
Furthermore, silk has a unique feel and luster, and has been awarded to human beings since ancient times. However, the fibers, films, sponges, and the like obtained by the present invention also exhibit characteristics according to the mixing ratio of silk. Fibers, films, sponges, etc., made of a composite of cellulose and silk, originally have a great deal of strength properties, and are industrially easy to manufacture. However, as its function, the above-mentioned characteristic functions of silk are exhibited in addition to the strength and hygroscopicity of cellulose. Furthermore, when molding chitin chitosan or a chitin chitosan derivative into a fiber, film or sponge using a composite produced as a material, the properties of silk are exhibited, and furthermore, the biological activity of chitin chitosan or chitin chitosan derivative Because it has added functions and antibacterial properties, it becomes a product that is truly suitable for an aging society.

[0008] When a material composed of chitin chitosan or a chitin chitosan derivative and silk is used as a material, depending on the characteristics of the polymer and the technique for molding these,
Fibers having a strength suitable for use in clothing and the like are somewhat insufficient. However, it is applicable to non-woven fabrics and the like that do not require much strength, and has applications in the field of veterinary medicine, including human medicine, or in the field of cosmetics, and its use is wide.

[0009] In molding, usually, a silk solution contains a portion in which the silk is truly dissolved and a finely dispersed silk.
Even in the case of ２０20%, if the method of the present invention is used, no obstruction or the like in the spinning nozzle is caused during molding. When the mixing ratio of silk is large and there is a risk of elution, if necessary, a denaturation step of the protein is provided at the time of molding so that the water-soluble silk is insolubilized and remains in the molded product. In this case, denaturation is performed according to a conventional method using an acid,
This is performed using an alkali, an organic solvent, or the like.

[0010]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

Example 1 (Preparation of silk solution) According to a conventional method, 10 g of refined silk was added to 200 cc of a solution containing 50% calcium chloride and kept at 125 ° C. for 5 hours while stirring. The dissolved silk solution is placed in a cellophane tube and dialyzed for 24 hours under running water.
Further, concentration is performed in the form of a dialysis tube. The silk solution concentration measured by the evaporation to dryness method was 9.3%.

[0011]

Example 2 (Preparation of chitin biscose) When dissolved in a mixed solvent of N, N-dimethylacetamide and lithium chloride so that the chitin concentration was 0.4%, the viscosity was 20%.
Chitin powder 10 which becomes 120 CPS at 120 ° C at 120 ° C
50 g of a 40% by weight aqueous solution of caustic soda was added to g, and the mixture was stirred at room temperature. The produced alkaline chitin was pressed to 4 times the weight of chitin. 2.4 ml of carbon disulfide is added to the squeezed alkali chitin under reduced pressure, and the mixture is stirred and reacted for 3 hours. 90 g of crushed ice was added to the obtained chitin zante, and the mixture was melted with stirring to obtain chitin biscote.
This chitin viscos had a chitin concentration of 5.4% and a falling ball viscosity of 72 seconds.

[0012]

Examples 3, 4, and 5 (Production of fiber) Cellulose viscos (cellulose concentration 8.1) produced by a known method
%), The silk aqueous solution obtained in Example 1 and the chitin viscos obtained in Example 2 are added and mixed with stirring. After stirring and mixing, the mixture was defoamed under reduced pressure, and a silk / chitin / cellulose conjugate fiber was obtained by a wet spinning method according to a usual method of producing a viscose rayon. The results are shown in [Table 1, Table 2, Table 3] below.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

Example 6 (Production of alkali chitin) To 71 g of chitin was added 400 g of a 48% by weight aqueous solution of caustic caustic soda, and the mixture was stirred and homogenized at room temperature. 8 crushed ice on the alkaline chitin
20 g was added and dissolved with stirring to obtain a chitin alkali solution. This chitin solution had a chitin concentration of 5.5%.

[0017]

Examples 7, 8, and 9 (Production of silk and chitin-cellulose conjugate fiber) Cellulose viscos (cellulose concentration 8.1%) produced by a known method was obtained in Example 1. A stirred mixed solution was prepared by combining the silk aqueous solution and the chitin alkali solution obtained in Example 6. After stirring and mixing, the mixture was defoamed under reduced pressure, and then a silk / chitin / cellulose conjugate fiber was obtained by a wet spinning method according to a usual method for producing viscos fibers.
However, in the case of Example 9, after spinning, the fiber was passed through a methanol bath, and then the next step was started. The results are shown below.

[0018]

[Table 4]

[0019]

[Table 5]

[0020]

[Table 6]

[0021]

Example 10 (Production of fiber from chitin chitosan derivative) To 30 g of propionylated chitosan was added 200 g of a 48% by weight aqueous solution of caustic soda, and the mixture was mixed and homogenized at room temperature.
415 g of crushed ice was added to the resulting propionylated chitosan alkali adduct and dissolved with stirring to obtain an alkali solution of propionylated chitin. This propionylated chitin solution had a concentration of 4.7%. To 48.51 parts of cellulose-biscosose (cellulose concentration 8.1%) and 3.21 parts of the silk aqueous solution obtained in Example 1, 3.56 parts of the alkaline solution of propionylated chitin were mixed with stirring. A homogeneous solution was made. After defoaming under reduced pressure, a silk / propionylated chitosan / cellulose conjugate fiber was obtained by a wet spinning method according to an ordinary method for producing a viscos rayon. The obtained fiber had a fineness of 1.8 d and a strength of 2 g / d / elongation of 18%.

[0022]

Industrial Applicability The present invention provides a polymer composite solution comprising silk, chitin chitosan and / or an acylated product thereof and cellulose, and a process for producing fibers, films or sponges on an industrial scale by a wet method. Method becomes possible, and it becomes possible to manufacture in large quantities at lower cost than before,
The manufactured product exhibits the bioactive function of chitin chitosan, so-called antibacterial property, and furthermore, the fiber, film, sponge or non-woven fabric, etc., due to the bioactive properties of silk, its unique feel and luster, and the strength dependent on cellulose. When molded into a molded product, it is powerful, has high antibacterial properties and physiological activities, is supplied in large quantities and at low cost, and is used for clothing or medical use.

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Claims (4)

[Claims] 1. Silk is composed of an alkali metal salt or an alkaline earth metal salt, a lower alcohol (including a case where the content is 0), and three components of water (when the alcohol content is 0, two components). Was dissolved in a mixed solvent and then dialyzed to remove salts and alcohols, or the solution was concentrated or concentrated to give a silk solution having a concentration of 2 to 20%, and a cellulose concentration of 3 to 1%.
A 0% biscos process cellulose solution, a chitin chitosan or an chitin chitosan acylated derivative having an alkali derivative concentration of 2 to 10%, and a single solution or a mixed solution thereof are mixed. To prepare a stock solution for molding, and then prepare a stock solution for molding having a silk ratio of 2 to 98% in the solute component, and optionally add a protein denaturation step along the way by a wet method to spin, form, and mold. A method for producing a polymer composite comprising a molded article such as fiber, film or sponge. 2. A polymer composite comprising a molded article such as a fiber, a film or a sponge produced by the production method according to claim 1. 3. Silk is composed of an alkali metal halide or an alkaline earth metal salt, a lower alcohol (including a case where the content is 0), and three components of water (when the alcohol content is 0, two components). Was dissolved in a mixed solvent and then dialyzed to remove salts and alcohols, or the solution was concentrated or concentrated to give a silk solution having a concentration of 2 to 20%, and a cellulose concentration of 3 to 1%.
A 0% biscos method cellulose solution, a chitin chitosan or a bistinated chitin chitosan or a chitin chitosan acylated derivative solution having a concentration of 2 to 10% of a chitin chitosan acylated derivative, and a single solution or a mixture thereof; The solution was mixed to form a stock solution, and then a stock solution having a silk ratio of 2 to 98% in the solute component was prepared. A method for producing a polymer composite comprising a film, a molded product such as a fiber, a film or a sponge by molding. 4. A polymer composite comprising a molded product such as fiber, film or sponge produced by the production method according to claim 3.