JPH08319475A - Polysaccharide antistatic agent - Google Patents

Abstract

(57) [Summary] [Structure] The constituent sugars are composed of five kinds of D-glucose, D-galactose, D-glucuronic acid, D-ribose and D-ribronic acid, and the constituent molar ratio is D-glucose: D-galactose: D-glucuronic acid: D-ribose: D-ribronic acid = 10: 1.8 to 2.9: 1.8 to
2.6: 0.5 to 1.7: 0.5 to 1.7, and a polysaccharide antistatic agent having an O-acetyl group content of 0 to 10% by weight. [Effect] An antistatic agent comprising a polysaccharide produced by a microorganism, which is more safe and biodegradable than conventional antistatic agents, is provided. Since the antistatic agent has these properties,
In particular, it is advantageous when incorporated into clothing, food packaging materials and tableware.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polysaccharide antistatic agent.

[0002]

2. Description of the Related Art A low molecular surface active agent as an antistatic agent is kneaded into plastic products or synthetic fibers, or is applied to the surface thereof, but is easily removed by cloth wiping or washing. However, there is a drawback that the effect does not last.

Therefore, synthetic polymer type antistatic agents such as polyethylene glycol, polyoxyethylenediamine, polyvinylbenzyltrimethylammonium chloride, polydiallyldimethylammonium chloride, sodium polystyrene sulfonate, etc., which have a permanent effect, have been attracting attention. Came.

However, considering the current environmental pollution problem, the above-mentioned polymer type antistatic agent has a problem that it is poor in biodegradability and safety because it is a synthetic polymer.

On the other hand, various polysaccharides such as dextran, pullulan, curdlan, xanthan gum, gellan gum and hyaluronic acid, which are the same polymers as synthetic polymers conventionally used as antistatic agents, are used in the fields of medicine, food and cosmetics. However, since these polysaccharides are natural products, have high safety, and have biodegradability, their use is expanding as substances friendly to living organisms and the global environment.

Natural polysaccharides are roughly classified into plant-derived,
There are those derived from animals and those derived from microorganisms, but those derived from microorganisms (polysaccharides produced by microorganisms) have been used more frequently than those derived from other sources in terms of supply and productivity.

[0007]

Under the circumstances described above, the present invention provides a polysaccharide of higher biodegradability and safety than synthetic polymer antistatic agents, which is supplied from plants or animals. The present invention provides an antistatic agent containing a microbial-produced polysaccharide, which is advantageous in terms of productivity.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the constituent sugars produced by Agrobacterium bacteria are D-glucose, D-galactose, D-glucuronic acid, D-ribose and It is composed of 5 kinds of D-libronic acid, and the molar ratio thereof is D-glucose: D-galactose: D-glucuronic acid: D-ribose: D-ribronic acid = 10: 1.8 to 2.9: 1. 8-2.6: 0.5
It was found that a polysaccharide having an O-acetyl group content of 0 to 10% by weight and an excellent antistatic ability of ~ 1.7: 0.5 to 1.7 has an antistatic ability. .

That is, the present invention is an antistatic agent comprising the above-mentioned polysaccharide as a component.

Hereinafter, the present invention will be described in detail. The polysaccharide used as the antistatic agent of the present invention preferably has the following characteristics in addition to the above characteristics.

Molecular weight: The molecular weight measured by gel filtration chromatography is about 1 × 10 ³ to 10 × 10 ⁶ .

The polysaccharide of the present invention also has the following properties. Properties: White fiber (lyophilized product).

Solubility: water, dilute acid, dilute alkali, DMSO
It is soluble in water and insoluble in methanol, ethanol and acetone.

[0014] The infrared absorption spectrum: 3400cm around ^{-1, 1620cm} around ^{-1, 1110cm} around ^-1, 125
0cm around ^-1, a peak of infrared absorption is observed at each of the vicinity of 2950 cm ^-1.

Color reaction: Positive in all of the phenol-sulfuric acid method, the carbazole-sulfuric acid method and the m-phenylphenol method.

The molecular weight of the polysaccharides used as the antistatic agent of the present invention, the types of constituent sugars, the constituent ratios thereof, the binding mode of the constituent sugars, etc. are determined by chromatographic analysis after acid hydrolysis, methylation analysis, Smith decomposition, etc. Can be specified by.

Next, specific examples of the method for specifying the polysaccharide of the present invention will be shown.

Measurement of molecular weight: "Asahip" manufactured by Asahi Kasei
ak GFA-7MF "column as a column, using GPC mode high performance liquid chromatography, using 0.1 M sodium nitrate aqueous solution as a mobile phase, and using pullulan of known molecular weight as a standard sample, a molecular weight-retention time standard curve was used. To measure.

Next, a method for producing the polysaccharide used as the antistatic agent of the present invention will be described. Usually, the polysaccharide of this case is Agrobacterium radiobacter TNM.
2 strains (Ministry of International Trade and Industry, Institute of Biotechnology, Institute of Biotechnology, Industrial Technology, Accession No. FERM BP-4393) or mutants thereof are used for microbial culture to collect from the culture. In this case, the mutant strain may be ultraviolet rays, radiation such as X-rays, or
Ethylmethanesulfonic acid (EMS), N-methyl-N '
It can be generated by known mutagenesis means such as chemical mutagens such as -nitro-N-nitrosoguanidine (MNNG).

The microbial culture using the above strain will be described in more detail.

As a medium for culturing the polysaccharide-producing microorganism used in the present invention, Agrobacterium (A
There is no particular limitation as long as a microorganism belonging to the genus Grobacterium can grow and it contains an appropriate amount of a carbon source, a nitrogen source, an inorganic salt and a trace nutrient source that produce the above-mentioned polysaccharide.

As carbon sources, glucose, lactose, maltose, xylose, mannitol, sucrose, rhamnose, arabinose, trehalose,
Raffinose is used. As the nitrogen source, synthetic compounds such as nitrates, ammonium salts and urea, polypeptone, corn steep liquor, yeast extract, meat extract, defatted soybean extract, peptides and natural organic substances such as amino acids are used.

As the inorganic salts, phosphates, potassium salts, sulfates, magnesium salts and the like are used. Iron salts, calcium salts, manganese salts and the like can be added to the medium, if necessary. In addition, as a micronutrient source,
Yeast extract and various vitamins are used.

The state of the medium may be solid or liquid. When a liquid medium is used, static culture may be used, but shaking culture and aeration-agitation culture can yield the polysaccharide used in the present invention in a higher yield. PH during culture
Is not particularly limited as long as it has a pH at which microorganisms can grow and produce the polysaccharide used in the present invention, but usually 4 to 8
PH is appropriate. The culture temperature is also not particularly limited, but usually 20 to 35 ° C is suitable. The culturing time is selected such that the production of the polysaccharide of the present invention reaches the maximum, but usually 1 to 7 days is appropriate.

The method for collecting the polysaccharide used in the present invention from the culture obtained by such a culture method is as follows:
A conventionally known method can be adopted. For example, first, cells are removed from the culture by centrifugation or filtration, and then an organic solvent such as methanol, ethanol, isopropanol, or acetone is added to the obtained culture solution to cause precipitation. Then, after dissolving the precipitate in water, dialysis is performed against water, and the dialysis inner solution is dried by a method such as ventilation drying, hot air drying, spray drying, drum drying, vacuum drying, and freeze drying. Recover sugar.

In addition to this collection method, a method is adopted in which components other than the polysaccharide used in the present invention are removed from the above culture solution by ultrafiltration, and the resulting concentrated solution is subjected to the above-mentioned drying step. May be. Furthermore, if necessary, a highly purified purified product can be obtained by purifying according to a general polysaccharide purification method. As the purification method, various column chromatography such as ion exchange, gel filtration, affinity, etc., precipitation with a quaternary ammonium salt, salting out, precipitation with an organic solvent, etc. are adopted.

The degree of polymerization of the polysaccharide used in the present invention can be changed by adjusting the conditions such as the medium composition at the time of production and the collecting method. Further, the collected product or the purified product can be hydrolyzed by using TFA, formic acid, hydrochloric acid or the like and adjusting the conditions. Further, as a specific method, suitable results can be obtained even if the degree of polymerization is changed by performing heating under pressure or ultrasonic treatment.

Therefore, the molecular weight of the above-mentioned polysaccharide is about 1 × 1.
It can be freely adjusted within the range of 0 ³ to 10 × 10 ⁶ .

The polysaccharides used in the present invention, which are collected from the culture by the above-mentioned microbial culture, are D-glucose, D-galactose, D-glucuronic acid and D-glucose.
It is composed of five constituent sugars, ribose and D-libronic acid, and the molar ratio of constituent sugars is D-glucose: D-galactose: D-glucuronic acid: D-ribose: D-libronic acid = 10: 1.8 to 2 .9: 1.8 to 2.6: 0.5 to
1.7: 0.5 to 1.7, O-acetyl group content is 0
It was revealed by the above-mentioned analytical means that it was in the range of -10% by weight.

The polysaccharides used in the present invention thus obtained have excellent antistatic ability, as will be shown in the Examples below.

[0031]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Production Example of the Polysaccharide of the Present Invention 100 ml of a medium having the composition shown in Table 1 was put in a Sakaguchi flask having a volume of 500 ml, sterilized by moist heat at 121 ° C. for 20 minutes, and then slant culture was separately performed on the medium having the composition shown in Table 1 culture)
Was doing Agrobacterium radiobacter-TNM
Two platinum strains (FERMBP-4393) were inoculated with one platinum loop and subjected to reciprocal shaking culture at 28 ° C. for 2 days at 28 strokes at 110 strokes per minute.

[0033]

[Table 1] Medium composition (% by weight) Sucrose 4 Sodium nitrate 0.1 Potassium monohydrogen phosphate 0.1 Magnesium sulfate heptahydrate 0.05 Iron sulfate heptahydrate 0.001 Yeast extract 0.4 pH 7

A 10 liter jar fermenter containing 6 liters of the same composition medium as in Table 1 and sterilized in the same manner was inoculated with 60 ml of the above-obtained culture solution at a temperature of 28 ° C. and an aeration rate of 6 liters. The culture was carried out with aeration and stirring for 94 hours under the condition of / min. The rotation speed was 200 rpm until the 19th hour of culture and 300r until the 51th hour.
pm, 300 rpm for 70 hours thereafter, and 400 rpm thereafter.

The obtained culture was diluted with water twice and the cells were removed by centrifugation. The obtained culture supernatant was subjected to cross-flow ultrafiltration until components other than polysaccharides such as residual medium components were removed. For ultrafiltration, an ultrafiltration system "UF-LM" manufactured by Tosoh Corporation.
SII ”(molecular weight cut-off: 3 × 10 ⁶ ) was used. The concentrated solution that did not permeate the ultrafiltration membrane was freeze-dried to obtain about 17 g of a single polysaccharide per liter of the medium.

The identity of the polysaccharide was confirmed by high performance liquid chromatography in GPC mode.
Asahi Kasei's "Asahipak GFA-7MF" was used as a column, high performance liquid chromatography using 0.1 M sodium nitrate aqueous solution as a mobile phase was used, and the result of measuring the molecular weight of the above-mentioned polysaccharide was the peak of the polysaccharide chromatograph. The retention time at the top showed a value corresponding to a molecular weight of about 2 × 10 ⁶ in the molecular weight-retention time standard curve prepared using pullulan of known molecular weight as a standard sample.

Further, with respect to this polysaccharide, each constituent sugar was hydrolyzed, and the hydrolyzate was subjected to liquid chromatography analysis as it was, and also subjected to fluorescent labeling for liquid chromatography analysis. The molar ratio of each constituent sugar was calculated from the calibration curve prepared in advance and the content of each constituent sugar determined from the peak height of each constituent sugar.
Galactose: D-Glucuronic acid: D-Ribose: D-
Libronic acid = 10.0: 2.1: 2.0: 1.0: 0.
It was 9.

In order to analyze the modification of the hydroxyl group of the polysaccharide, 0.01M potassium hydroxide and 0.13M potassium hydroxide were used.
The polysaccharide obtained above was deacylated in an aqueous solution of potassium chloride at room temperature for 6 hours. As a result of performing high performance liquid chromatography analysis on the treated sample,
A peak having the same retention time as the peak when the aqueous potassium acetate solution was analyzed was detected. The O-acetyl group content of the polysaccharide was determined from the calibration curve prepared in advance and the peak height, and it was about 8% by weight based on the whole polysaccharide. As a result of measuring the infrared absorption spectrum of the deacylated polysaccharide, the peak around 1730 cm ^-1 disappeared.

Safety Data When the safety data of the polysaccharide obtained in the above Production Example was measured, the following results were obtained. Acute oral toxicity (rat, LD ₅₀ ):> 5000 mg / k
g (actually harmless)

[0040]

Example 1 (Evaluation of Antistatic Ability of Polysaccharide) A 1% (w / v) aqueous solution of the polysaccharide obtained in the Production Example was poured into a glass petri dish (diameter 90 mm × height 10 mm) and heated at 50 ° C. 30 μm on a petri dish after drying with
The film resistance of the DIGITAL EL film was measured by forming a film of a certain degree and leaving it at 25 ° C and 40% humidity overnight.
ECTOMER (ADVANTEST, TR8
652) was measured under the same temperature and humidity conditions to obtain the surface resistivity. For comparison, pullulan (manufactured by Hayashibara Co., Ltd.), which is a commercially available polysaccharide produced by microorganisms and which has a low viscosity, is easy to handle, and is useful as a filming agent, was similarly treated.

The results are shown in Table 2.

[0042]

Table 2 Surface resistivity (Ω) Polysaccharide obtained in Production Example 2.14 × 10 ¹⁰ pullulan 1.55 × 10 ¹⁰ blank 1.60 × 10 ¹²

As is clear from these results, in a petri dish having a film formed on its surface with the polysaccharide used in the present invention,
Since the surface resistivity is lower than that of a blank (no sample coating) petri dish, it can be seen that the polysaccharide used in the present invention has the same antistatic ability as pullulan.

[0044]

Example 2 Water: 99 g of polysaccharide obtained in Production Example
An aqueous solution was prepared by dissolving 0 g. In addition, pullulan (PF20, manufactured by Hayashibara) and hard dodecylbenzenesulfonic acid Na salt (manufactured by Teika) were similarly prepared as aqueous solutions. The soft dodecylbenzenesulfonic acid Li salt (manufactured by Teika) was prepared in the same manner with methanol as the solvent.

These solutions were impregnated and coated on woodfree paper so that the coating amount after drying was 2.0 g / m ^2, and then dried at 70 ° C. to obtain a conductive sheet. The surface electrical resistance values of the four types of conductive sheets obtained were measured under the conditions of 20 ° C. and a relative humidity of 60%, and the results are shown in Table 4.

[0046]

[Table 4] Surface electric resistance value Polysaccharide of the present invention 5.0 × 10 ¹³ pullulan 0.88 × 10 ¹³ hard type dodecylbenzenesulfonic acid Li salt 0.24 × 10 ¹³ soft type dodecylbenzenesulfonic acid Na salt 58 x 10 ¹³

[0047]

Example 3 To 88 g of purified water, 1.0 g of the polysaccharide obtained in the production example and 5.0 g of glycerin were added to prepare a 70 ° C. aqueous solution. Then cetyl alcohol, 2.
0 g, silicone oil, 3.0 g, polyoxyethylene (1
(0 mol) oleyl alcohol ether (1.0 g) was mixed, heated and melted, and the mixture was added to the above aqueous solution while stirring well, and further cooled to room temperature while stirring.

Using the hair rinse thus obtained, the hair after washing was rinsed and dried with a drier, but even if it was brushed in a room where the humidity was 30% and the temperature was 20 ° C. There was no electrostatic damage such as clinging to.

[0049]

Example 4 1% (w / v) of the polysaccharide obtained in the production example
A solution obtained by gradually mixing 50 ml of an aqueous solution with 50 ml of ethanol was put in a sprayer and sprayed on the lining of the skirt (made of polyester) at a rate of 2.5 g / m ² .

I wore this skirt with a lining and walked indoors at a humidity of 40% and a temperature of 15 ° C. However, clinging of the skirt due to static electricity did not occur.

[0051]

EFFECTS OF THE INVENTION According to the present invention described above, among polysaccharides having higher biodegradability and safety than synthetic polymer antistatic agents, those of plant-derived or animal-derived ones have higher productivity and productivity. In addition to being able to provide an antistatic agent that contains microbial-produced polysaccharides that are advantageous in terms of use, it can be used as an antistatic agent for synthetic fibers and plastic products, and is also applied to the coating field such as antistatic coating and conductive coating. Is also possible.

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Claims (1)

[Claims] 1. The constituent sugar is composed of five kinds of D-glucose, D-galactose, D-glucuronic acid, D-ribose and D-ribronic acid, and the constituent molar ratio is D-glucose: D-galactose: D-glucuronic acid: D-ribose: D-ribronic acid = 10: 1.8 to 2.9: 1.8
-2.6: 0.5-1.7: 0.5-1.7, and the polysaccharide type antistatic agent whose O-acetyl group content is 0-10 weight%.