KR102192110B1 - Bio-leather Material Containing Bacterial Cellulose Fiber and a Preparation Method thereof - Google Patents

Abstract

The present invention relates to a bio-leather material manufactured using bacterial cellulose fibers and a manufacturing method thereof. The bio-leather material contains a specific content of soy protein fraction and bacterial cellulose fibers modified with a hydroxyl-containing compound, so that durability and flexibility are improved, thereby being usefully used as an interior material such as clothing, furniture, building interior materials, automobile interior materials and the like.

Description

[Bio-leather Material Containing Bacterial Cellulose Fiber and a Preparation Method thereof]

The present invention relates to a bio-leather material manufactured using bacterial cellulose fibers and a method for manufacturing the same, and in particular, a bio-leather containing bacterial cellulose fibers having excellent mechanical properties and strength by being modified with a soy protein fraction and a hydroxyl-containing compound. It relates to a material and a method of manufacturing the same.

Petroleum-based synthetic fibers, which are widely used not only in clothing but also in industrial fields, discharge a lot of pollutants in the production process, and are not decomposed in the natural environment when discarded, but remain semi-permanently, becoming a serious factor of environmental pollution. As environmental awareness increases around the world, interest in natural fibers using eco-friendly polymers is increasing in order to solve such problems.

Bacterial cellulose (BC), which is now represented as a natural polymer, is a promising and sustainable nanofiber material with the same chemical structure as plant-based cellulose. Unlike petroleum-based fossil resources, there is no concern about depletion and production costs are low. In addition, it is an eco-friendly material with infinite potential as a biodegradable material that is decomposed into glucose (glucose), which is a constituent molecular unit in its natural state.

However, bacterial cellulose has a chain structure in which glucose is strongly bonded through hydrogen bonds between molecules, and its industrial applicability is limited due to relatively low mechanical properties compared to synthetic fibers made of synthetic polymers.

In order to solve this problem, a technology for improving the tensile strength of fibers by adding carbon-based nanomaterials such as graphene, carbon nanotubes, and carbon nanofibers to natural polymer resins such as cellulose has been developed. However, since the additives do not bond well at the interface with the polymer resin, it is difficult to achieve an expected improvement in physical properties, and even if mechanical properties are achieved, there is a limit in that the flexibility of the fiber material is reduced.

Therefore, there is a need to develop a fiber material that is eco-friendly, including natural polymers, and that can simultaneously realize excellent mechanical properties and flexibility.

Republic of Korea Patent Publication No. 2018-0104799

An object of the present invention is to provide a natural fiber having excellent mechanical properties such as tensile strength and elongation, excellent durability, and excellent flexibility, and a method for manufacturing the same.

In addition, an object of the present invention is to provide a bio leather material using the natural fibers.

To achieve the above object,

The present invention in one embodiment,

Contains bacterial cellulose fibers,

The bacterial cellulose fiber provides a bio-leather material, which is modified with a soy protein fraction and a hydroxyl-containing compound.

In addition, the present invention in one embodiment,

Immersing the bacterial cellulose hydrogel in a solution containing a soy protein fraction and a hydroxyl group-containing compound to prepare a modified bacterial cellulose hydrogel; And

It provides a method for producing a bio-leather material comprising the step of preparing modified bacterial cellulose fibers by drying the modified bacterial cellulose hydrogel.

The bio-leather material according to the present invention has excellent durability and flexibility, including bacterial cellulose fibers modified with soy protein fractions and hydroxyl-containing compounds, and thus can be usefully used as interior materials such as clothing, furniture, building interior materials, and automobile interior materials. have.

In the present invention, various modifications may be made and various embodiments may be provided, and specific embodiments will be illustrated in the drawings and described in detail.

However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In the present invention, terms such as "comprises" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or a combination thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance the possibility.

The present invention relates to a bio-leather material manufactured using bacterial cellulose fibers and a method for manufacturing the same.

Recently, while interest in bacterial cellulose (BC), which is represented by a natural polymer, is increasing, research to improve low mechanical properties is being actively conducted in order to expand the range of application of bacterial cellulose (BC) fibers. As an example, conventional technologies using additives such as carbon nanomaterials have been developed. However, the above techniques are limited in that the effect of improving physical properties is insignificant because bacterial cellulose (BC) and additives are not well bonded at the interface, and the flexibility of the material is reduced even if desired properties are achieved.

Accordingly, the present invention provides a bio-leather material using bacterial cellulose fibers that simultaneously satisfy mechanical properties and flexibility, and a method for manufacturing the same.

The bio-leather material according to the present invention has excellent durability and flexibility, including the soy protein fraction and bacterial cellulose fiber modified with a hydroxyl-containing compound, so it can be usefully used as an interior material such as clothing, furniture, building interior materials, and automobile interior materials. There is an advantage.

Hereinafter, the present invention will be described in more detail.

Bio leather material

The present invention in one embodiment,

Contains bacterial cellulose fibers,

The bacterial cellulose fiber provides a bio-leather material, which is modified with a soy protein fraction and a hydroxyl-containing compound.

The bio-leather material according to the present invention includes bacterial cellulose fibers (BC), which are natural fibers, wherein the bacterial cellulose fibers (BC) are a kind of fibrin produced by cultivation such as acetic acid bacteria, and general plants Fibers are made of cellulose, hemicellulose, lignin, etc., but bacterial cellulose has the advantage of not having to remove impurities separately because only pure cellulose is made.

In addition, the bacterial cellulose fiber (BC) has a structure modified with a soy protein fraction and a hydroxyl-containing compound. Specifically, in the bacterial cellulose fiber (BC), a soy protein fraction and a hydroxyl group-containing compound are inserted between a plurality of microfibrils (micro fibrilles) constituting the bacterial cellulose fiber (BC) to coexist inside and outside the fiber. It can take the form of

In this case, the total content of the soy protein fraction and the hydroxyl group-containing compound contained in the modified bacterial cellulose fiber may have a specific range that simultaneously satisfies the mechanical properties and flexibility of the modified bacterial cellulose fiber. Specifically, the total content of the soy protein fraction and the hydroxyl group-containing compound may be 10 to 40 parts by weight, based on 100 parts by weight of bacterial cellulose fibers (BC), and more specifically, 10 to 30 parts by weight based on 100 parts by weight of the bacterial cellulose fibers. Parts, 10 to 25 parts by weight, 10 to 20 parts by weight, 10 to 15 parts by weight, 20 to 35 parts by weight, 11 to 28 parts by weight, 11 to 14 parts by weight, or 25 to 29 parts by weight.

In addition, the hydroxyl group-containing compound may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the soy protein fraction, and specifically, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less based on 100 parts by weight of the soy protein fraction, It may be included in 10 parts by weight or less, 2 to 7 parts by weight, 5 to 40 parts by weight, 20 to 50 parts by weight, 20 to 40 parts by weight, 25 to 35 parts by weight, or 28 to 32 parts by weight, including a hydroxyl-containing compound If not, it is excluded.

The present invention can improve the mechanical properties and stiffness of the bacterial cellulose fibers at the same time by modifying the bacterial cellulose fibers with the soy protein fraction and the hydroxyl group-containing compound satisfying the above content range, through which bio leather containing the bacterial cellulose fibers Both the durability and flexibility of the material can be improved.

In addition, the bio leather material may have a certain thickness, which may be adjusted according to the content and/or content ratio of the soy protein fraction and the hydroxyl-containing compound, or in some cases, according to the thickness of the bacterial cellulose fiber itself. . Here, the thickness of the bacterial cellulose fiber itself may depend on the cultivation time of acetic acid bacteria or the like during fiber production.

The average thickness of the bio leather material may be, for example, 0.03 mm to 0.5 mm, more specifically 0.035 mm to 0.4 mm, 0.040 mm to 0.3 mm, 0.045 mm to 0.25 mm, 0.040 mm to 0.1 mm, 0.040 mm to 0.08 mm, 0.06 mm to 0.25 mm, 0.06 mm to 0.1 mm, 0.06 mm to 0.08 mm, 0.08 mm to 0.10 mm to 0.25 mm, 0.12 mm, 0.15 mm to 0.2 mm, 0.15 mm to 0.3 mm or 0.18 mm to It can be 0.25 mm. By controlling the average thickness of the bio leather material of the present invention within the above range, the tensile strength and strength of the modified bacterial cellulose fibers can be more optimized.

As an example, when measuring mechanical properties according to KR K 0521, the bacterial cellulose fiber of the present invention may have a tensile strength of 20N to 200N, and an elongation of 1% to 10%. For example, the bacterial cellulose fiber is modified with a soy protein fraction of a specific content and a hydroxyl-containing compound, so that the tensile strength is 20N to 200N, 30N to 40N, 31N to 39N, 33N to 37N, when measuring mechanical properties according to KR K 0521, 35N to 45N, 30N to 50N, 35N to 60N, 50N to 100N, 80N to 110N, 100N to 150N, 130N to 170N, 150N to 200N, or 180N to 200N. In addition, the bacterial cellulose fiber has an elongation of 1% to 8%, 2% to 10%, 2% to 8%, 2% to 5%, 4% to 8%, 2.5% to 4%, or 5.5% to 7 It can be %.

As another example, the bacterial cellulose fiber has improved stiffness along with mechanical properties, and thus may exhibit a high stiffness of 40 mm to 70 mm when measuring stiffness according to KR K 0538, specifically 40 mm to 67 mm, 40 mm to 65 mm, 40 mm to 60 mm, 45 mm to 65 mm, 60 mm to 66 mm, 62 mm to 65 mm, or 44 mm to 50 mm. This may be an improved value of 1 to 20%, specifically 5 to 10%, compared to the untreated bacterial cellulose fiber not modified with the soybean protein fraction and the hydroxyl-containing compound.

On the other hand, the soy protein fraction used in the present invention is obtained by isoelectric precipitation of protein in an extract obtained by extracting skim soybeans with water or a weak alkaline solution, and may have a powder form, and may have a powder form; protein; Inorganic substances such as sodium (Na), potassium (K), calcium (Ca), iron (Fe), and magnesium (Mg); And moisture and the like, and may be used without particular limitation as long as it has a constitution in which the content of the protein is within about 90%.

Further, the hydroxyl group-containing compound may be used without particular limitation as long as it is a compound containing two or more hydroxyl groups (-OH group). For example, as the hydroxyl-containing compound, glycerol, ethylene glycol, propylene glycol, and the like may be used, and glycerol may be preferably used.

Manufacturing method of bio leather material

In addition, the present invention in one embodiment,

Immersing the bacterial cellulose hydrogel in a solution containing a soy protein fraction and a hydroxyl group-containing compound to prepare a modified bacterial cellulose hydrogel; And

It provides a method for producing a bio-leather material comprising the step of preparing modified bacterial cellulose fibers by drying the modified bacterial cellulose hydrogel.

The method of manufacturing a bio-leather material according to the present invention includes a step of producing a modified bacterial cellulose fiber by modifying a bacterial cellulose hydrogel with a solution containing a soy protein fraction and a hydroxyl group-containing compound, and then drying the modified hydrogel. do.

Specifically, the manufacturing method includes modifying the bacterial cellulose hydrogel by immersing it in a solution containing a soy protein fraction and a hydroxyl group-containing compound.

At this time, in the bacterial cellulose hydrogel, a plurality of micelles formed by collecting cellulose chains may be aggregated to form microfibrils (micro fibrilles), and the formed microfibrils may be collected to form a porous woven fabric or It may have a fabric shape such as a nonwoven fabric.

In addition, the bacterial cellulose hydrogel is a weakly basic solution (pH 9 to 11) at a concentration of 5 to 10% by weight before being immersed in a solution containing a soy protein fraction and a hydroxyl group-containing compound, such as an aqueous sodium hydroxide (NaOH) solution, 10 to 60 while immersed in an aqueous solution of pH 9 to 11 such as potassium hydroxide (KOH) aqueous solution and swelled, or immersed in a solution containing protein fractions and hydroxyl group-containing compounds whose pH is adjusted to 9 to 11 For a minute, specifically 20 to 40 minutes of ultrasonic irradiation, swelling and modification may be performed simultaneously and/or continuously. Here, the "swollen form" may mean a state in which the hydrogel absorbs the solvent and the amorphous region between the micelles and the micelles in the fiber swells.

In addition, the solution containing the soy protein fraction and the hydroxyl group-containing compound may contain a soy protein fraction of a predetermined concentration. Specifically, the solution may contain a soy protein fraction at a concentration of 10 to 60 g/L, and more specifically, a soy protein fraction of 10 to 55 g/L, 10 to 50 g/L, and 10 to 40 g /L, 15 to 60 g/L, 20 to 60 g/L, 15 to 55 g/L, 15 to 30 g/L, 20 to 40 g/L, 30 to 50 g/L, 40 to 60 g/ L or 45 to 55 g/L.

Further, the hydroxyl group-containing compound may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the soy protein fraction, and specifically, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight based on 100 parts by weight of the soy protein fraction. It may be included in parts by weight or less, 2 to 7 parts by weight, 5 to 40 parts by weight, 20 to 50 parts by weight, 20 to 40 parts by weight, 25 to 35 parts by weight, or 28 to 32 parts by weight, and does not include a hydroxyl-containing compound. If not, it is excluded.

The present invention can improve the mechanical properties and stiffness of the bacterial cellulose fibers at the same time by modifying the bacterial cellulose fibers with the soy protein fraction and the hydroxyl group-containing compound satisfying the above content range, through which bio leather containing the bacterial cellulose fibers The durability and flexibility of the material can be improved.

In addition, the method for producing a bio leather material according to the present invention includes the step of preparing modified bacterial cellulose fibers by drying the modified hydrogel.

Specifically, drying of the modified bacterial cellulose fibers may be introduced into a drying oven and performed at a temperature of 25±2° C. for 20 to 30 hours, but is not limited thereto.

Bio leather material uses

Furthermore, the present invention in one embodiment,

It provides a product using the bio leather material according to the present invention.

As described above, the bio-leather material according to the present invention has excellent durability and flexibility, including bacterial cellulose fibers having high mechanical properties and strength by being modified with a specific content of soy protein fraction and a hydroxyl-containing compound. A field in which a leather material having flexibility and flexibility is used, specifically, clothing products such as clothing, shoes, bags, and accessories that can directly contact the user's skin; Alternatively, it may be usefully used in interior fields such as furniture, architectural interior materials, and automobile interior materials.

Hereinafter, the present invention will be described in more detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

Example 1 to 7.

First, an HS medium consisting of 20 g/L of glucose, 5 g/L of yeast and 3 g/L of peptone was prepared, and a bacterial cellulose hydrogel obtained from scoby was 1:5 (w/v). It was added to the prepared culture medium in a liquid ratio of. Then, static cultivation was performed for 7-14 days at 26°C in an incubator (SI-600R, JEIO TECH Co., Daejeon, Korea). After incubation, the prepared bacterial cellulose hydrogel was washed with distilled water at 100° C. for 5 minutes. Then, the bacterial cellulose hydrogel was bleached with a 1:10 (w/v) H ₂ O ₂ solution at 90° C. for 60 minutes in a water bath (110 rpm).

Separately, the soybean protein fraction (SPI) and glycerol were dissolved in distilled water, stirred for 15 minutes, and then the pH was adjusted to 10.5±0.2 using 1N sodium hydroxide (NaOH) aqueous solution. Then, the pH-adjusted solution was stirred at 70° C. for 20 minutes at 80 rpm in a constant temperature water bath, and then cooled to room temperature. Here, the concentrations of the soy protein fraction and glycerol in the solution are as shown in Table 1 below.

Thereafter, the previously bleached bacterial cellulose hydrogel was added to the solution at a ratio of 1:20 (w/v), followed by sonication for 30±2 minutes under the conditions of a fixed frequency of 45 kHz and 120 W to swell. The swollen bacterial cellulose hydrogel was taken out of the solution, put in a drying oven, and dried at 25±1° C. for 24 hours to prepare a bio leather material.

Soy protein fraction
(SPI) Glycerol
(Based on 100 parts by weight of SPI) Average thickness Average weight Example 1 10 g/L 30 parts by weight 0.044 mm 0.168 g Example 2 20 g/L 30 parts by weight 0.058 mm 0.222 g Example 3 30 g/L 30 parts by weight 0.046 mm 0.238 g Example 4 40 g/L 30 parts by weight 0.070 mm 0.304 g Example 5 50 g/L 30 parts by weight 0.070 mm 0.340 g Example 6 50 g/L 30 parts by weight 0.212 mm 0.580 g Example 7 50 g/L 5 parts by weight 0.070 mm 0.187 g

Comparative example 1 to 4.

A bio-leather material was prepared in the same manner as in Example 1, except that the concentrations of the soy protein fraction and glycerol in the solution were adjusted as shown in Table 2 below.

Soy protein fraction
(SPI) Glycerol
(Based on 100 parts by weight of SPI) Average thickness Average weight Comparative Example 1 - - 0.02 mm 0.012 g Comparative Example 2 100 g/L 30 parts by weight 0.74 mm 0.397 g Comparative Example 3 50 g/L - 0.070 mm 0.385 g Comparative Example 4 50 g/L 100 parts by weight 0.160 mm 0.525 g

Experimental example One.

In order to evaluate the mechanical properties and flexibility of the bio-leather material according to the present invention, the tensile strength of the material (6 cm wide x 13 cm long) is measured according to KS K 0521, and the stiffness of the material is measured according to KS K 0538. And the results are shown in Table 3.

Tensile strength [N] Lecture rate [%] Example 1 32.54 65 Example 2 29.20 66 Example 3 34.69 64 Example 4 39.40 64 Example 5 41.55 65 Example 6 184.24 46 Example 7 45.47 66 Comparative Example 1 Not measurable 76 Comparative Example 2 26.46 67 Comparative Example 3 Not measurable 73 Comparative Example 4 Not measurable 65

As shown in Table 3, it can be seen that the bio leather material according to the present invention has excellent durability and flexibility.

Specifically, it was found that the bio-leather material prepared in Examples has a high tensile strength of 28N to 185N, and the tensile strength tends to improve as the content of the soy protein fraction and the average thickness of the material increase. Confirmed to have. On the other hand, it was confirmed that the bio-leather material prepared in the comparative example cannot measure the tensile strength or has a significantly lower value than the result value of the example.

In addition, it was confirmed that the bio-leather material of the example had a "strength" of 45 mm to 66 mm, which represents the softness and strength of the leather as a resistance value against bending. This means an improvement of 5% to 10% compared to the bio-leather material of Comparative Example 1 comprising the soy protein fraction and the untreated bacterial cellulose fiber, which is not modified with glycerol.

From these results, it can be seen that the bio-leather material according to the present invention includes a soy protein fraction of a specific content and bacterial cellulose fibers modified with a hydroxyl-containing compound to provide excellent durability and flexibility.

Claims (17)

Consisting of a plurality of microfibrils, including a soybean protein fraction and a hydroxy group-containing compound is inserted bacterial cellulose fibers between the plurality of microfibrils,
A bio leather material in which the microfibrils are gathered to form a fabric.
delete The method of claim 1,
The total content of the soy protein fraction and the hydroxyl-containing compound is 10 parts by weight to 40 parts by weight based on 100 parts by weight of bacterial cellulose fibers.
The method of claim 1,
The content of the hydroxyl-containing compound is 50 parts by weight or less based on 100 parts by weight of the soy protein fraction.
The method of claim 1,
The hydroxyl group-containing compound is one or more bio leather materials selected from the group consisting of glycerol, ethylene glycol and propylene glycol.
The method of claim 1,
Bio leather material, characterized in that the average thickness of the bio leather material is 0.03 mm to 0.5 mm.
The method of claim 1,
Bio-leather material is a bio-leather material having a tensile strength of 20N to 200N according to KS K 0521.
The method of claim 1,
The bio leather material is a bio leather material with a strength of 40 mm to 70 mm according to KS K 0538.
Preparing a modified bacterial cellulose hydrogel by immersing the bacterial cellulose hydrogel in a solution containing a soy protein fraction and a hydroxyl-containing compound; And
A method for producing a bio-leather material comprising the step of drying the modified bacterial cellulose hydrogel to prepare modified bacterial cellulose fibers.
The method of claim 9,
The concentration of the soy protein fraction is 10 to 60 g / L of the method for producing a bio leather material.
The method of claim 9,
The content of the hydroxyl group-containing compound is 50 parts by weight or less based on 100 parts by weight of the soy protein fraction.
The method of claim 9,
The step of preparing the modified bacterial cellulose hydrogel is a method of manufacturing a bio leather material performed by irradiating ultrasonic waves on the immersed bacterial cellulose hydrogel.
The method of claim 12,
Ultrasound is a method of manufacturing a bio leather material performed for 10 to 60 minutes.
The method of claim 9,
A method for producing a bio leather material, wherein the solution containing the soy protein fraction and the hydroxyl group-containing compound has a pH of 9 to 11.
A clothing product using the bio-leather material according to claim 1.
The method of claim 15,
The clothing product is a clothing product including one or more miscellaneous goods selected from the group consisting of shoes, bags, and accessories.
An interior product using the bio leather material according to claim 1.