KR102681081B1 - Anti-static Composition and Complex Sheet Using the Same - Google Patents

Abstract

The present invention relates to a composite sheet having a long-term antistatic effect, clothing using the same, and an antistatic composition for producing the same. Provided in one aspect of the present invention, it includes a laminated sheet in which a non-woven fabric and a breathable film are laminated, and an anti-static layer formed by applying an anti-static composition containing chitosan and an organic binder having an ionic group on one or both sides of the laminated sheet. Since the composite sheet it contains has a permanent anti-static effect, it can be usefully used in the production industry of protective clothing, anti-static clothing, sports clothing, work clothing, and pest control clothing.

Description

Anti-static composition and complex sheet using the same {Anti-static Composition and Complex Sheet Using the Same}

The present invention relates to a composite sheet whose antistatic effect does not change over a long period of time, clothing using the same, and an antistatic composition capable of producing the same.

When wearing medical or industrial protective clothing, it is very important to prevent static electricity generated from the fibers to provide a comfortable fit for workers or to minimize electrical effects on surrounding devices. For example, the generation of static electricity can cause machine malfunction, and the static electricity generated on the surface of protective clothing, anti-static clothing, etc. can cause fine dust to attach to the surface and flow into the workplace, causing contamination inside the workplace. There is a risk.

Conventional antistatic methods to solve the above problem include weaving fabric by mixing carbon-containing yarns or treating the surface of the fiber with a water-based antistatic agent. However, in the case of carbon fiber, it can only be applied to fabrics in a limited way due to problems with coloring and contamination, and there is also the problem of low flexibility of the fabric. In addition, nonwoven fabrics or films treated with a water-based antistatic agent provide a short-term charging effect, but there is a problem in that the charging effect disappears over time.

For example, U.S. Patent No. 5,641,859 discloses a method using water-soluble conductive polyaniline, but there is a problem in that long-term antistatic performance is still insufficient due to low electrical conductivity.

Therefore, there is a demand for the development of new protective clothing that has long-term antistatic properties, that is, permanent antistatic properties, as well as flexible and soft properties as a protective clothing.

One object of the present invention is to provide a composite sheet with semi-permanent antistatic properties, clothing using the same, and an antistatic composition for producing the same.

Another object of the present invention is to provide a new anti-static composite sheet and clothing using the same, which have semi-permanent anti-static properties and at the same time give a soft texture like everyday clothes.

The composite sheet according to the present invention includes an antistatic layer formed by applying an antistatic composition containing chitosan and an organic binder having an ionic group on one or both sides of a laminated sheet in which a nonwoven fabric and a breathable film are laminated.

In one example of the present invention, the chitosan having an ionic group in the antistatic composition may be chitosan substituted with a quaternary ammonium group.

In one example of the present invention, the antistatic composition may further include a conductive material.

In one example of the present invention, the conductive material may be one or two or more selected from conductive polymers, conductive metal particles, carbon black, graphite, and carbon nanofibers.

In one example of the present invention, the antistatic composition includes 0.1 wt% to 10 wt% of chitosan having an ionic group, 0.1 wt% to 30 wt% of an organic binder, and 0.5 wt% to 10 wt of a conductive material, relative to the weight of the entire composition. It can be included as a %.

In one example of the present invention, the weight ratio of chitosan and the conductive material having an ionic group in the antistatic composition may be 1:0.05 to 1:50.

In one example of the present invention, the breathable film may be a polyolefin-based breathable film.

In one example of the present invention, the nonwoven fabric may be made of one or more selected from polypropylene, polyester, polyethylene, and copolymers thereof.

The composite sheet according to the present invention has an antistatic property of 2.8×10 ¹⁰ according to EN1149-1. It may be Ω or less.

The antistatic composition according to the present invention includes chitosan and an organic binder having an ionic group.

In one example of the present invention, the chitosan having the ionic group may be chitosan substituted with a quaternary ammonium group.

In one example of the present invention, the antistatic composition may further include a conductive material.

In one example of the present invention, the conductive material may be one or two or more selected from conductive polymers, conductive metal particles, carbon black, graphite, and carbon nanofibers.

In one example of the present invention, the antistatic composition includes 0.1 wt% to 10 wt% of chitosan having an ionic group, 0.1 wt% to 30 wt% of an organic binder, and 0.5 wt% to 10 wt of a conductive material, relative to the weight of the entire composition. It can be included as a %.

In one example of the present invention, the weight ratio of chitosan and the conductive material having an ionic group in the antistatic composition may be 1:0.05 to 1:50.

Clothing according to the present invention is selected from protective clothing, anti-static clothing, sports clothing, work clothing, chemical clothing, dust-proof clothing, and pest control clothing made from the composite sheet.

The antistatic composition according to the present invention has the effect of maintaining the antistatic effect even with the passage of time, unlike existing methods that have the disadvantage that the antistatic effect disappears over time.

In addition, the composite sheet formed by applying the anti-static composition to one or both sides of a laminated sheet of non-woven fabric and a breathable film, and the clothing made from the composite sheet have excellent flexibility and are comfortable to wear, and also have excellent anti-static properties. , which has the effect of maintaining its characteristics.

The present invention will be described in more detail through examples below. However, the following examples are only a reference for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Additionally, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe specific embodiments and is not intended to limit the invention.

Additionally, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.

Additionally, when a part is said to “include” a certain component, this does not mean excluding other components, but may include other components, unless specifically stated to the contrary.

One aspect of the present invention for achieving the above object is a composite comprising an antistatic layer formed by applying an antistatic composition containing chitosan and an organic binder having an ionic group on one or both sides of a laminated sheet in which a nonwoven fabric and a breathable film are laminated. Sheets are provided.

The thickness of the antistatic layer may be 0.1 to 10 ㎛, preferably 0.1 to 5 ㎛, but is not limited thereto, and the thickness may be adjusted depending on the line width, required resistance, and post-processing conditions of the composite sheet to be implemented.

Chitosan having an ionic group in the antistatic composition may be chitosan substituted with a quaternary ammonium group. Chitosan substituted with a quaternary ammonium group is one in which the amine group of chitosan is replaced with a quaternary ammonium group.

By including chitosan having the ionic group, the antistatic layer not only has excellent antistatic properties, but also has the property that the antistatic properties are maintained without change over time. Therefore, the composite sheet also has excellent antistatic properties, and has the property of maintaining the antistatic effect without changing. In particular, in addition to the antistatic retention properties, the flexibility of the composite sheet is very excellent, so it can have the effect of significantly improving wearing comfort. there is.

In the present invention, the organic binder is not limited as long as it is a polymer used in this field, but for example, polyvinyl acetate, polycarbonate, polyacrylate, polybutylate, polyether, polyester, polyurethane, polyacrylic-urethane copolymer. Examples include polymers and copolymers of vinyl acetate-vinyl alcohol-vinyl chloride, but are not necessarily limited thereto.

The antistatic composition may further include a conductive material, and is not particularly limited as long as it is a conductive material. For example, the conductive material may be one or two or more selected from conductive materials such as conductive polymers, conductive metal particles, carbon black, graphite, and carbon nanofibers.

As examples of the conductive polymer, polyaniline, polypyrrole, polythiophene, poly(3,4-ethylenethiophene), or derivatives thereof may be used.

The conductive metal particles are not limited as long as they are conductive metal particles, but for example, single particles such as copper, nickel, zinc, brass, gold, silver, etc., mixtures of copper, nickel, zinc, brass, etc., or surfaces of these metals. It may be treated particles. The average particle diameter of the metal particles may be 0.001 ㎛ to 100 ㎛.

The carbon black may be natural carbon black or artificial carbon black, and its particle size may be 0.01 ㎛ to 100 ㎛ or 0.1 ㎛ to 50 ㎛.

The chitosan having the ionic group may be included in an amount of 0.1 wt% to 10 wt%, 0.5 wt% to 5 wt%, or 1 wt% to 3 wt%, based on the weight of the entire antistatic composition including the solvent. The organic binder may be included in the range of 0.1 wt% to 30 wt%, preferably 1 wt% to 25 wt%, or 5 wt% to 20 wt%, based on the weight of the total composition, but is limited to this as long as the purpose of the present invention is achieved. I never do that.

Additionally, the conductive material may be included in an amount of 0.5 wt% to 10 wt%, 1 wt% to 8 wt%, or 2 wt% to 5 wt% based on the total weight of the antistatic composition.

The remaining content of the antistatic composition may be a solvent, and the solvent is not limited thereto, but is propylene glycol monomethyl ether acetate, toluene, ethyl acetate, butyl acetate, acetone, methanol, butyl carbitol, butyl carbitol acetate, butyl It may be one or more selected from the group consisting of cellosolve, butyl cellosolve acetate, terpineol, and water.

In one aspect of the present invention, the weight ratio of chitosan having an ionic group and the conductive material may be 1:0.05 to 1:50 or 1:0.1 to 1:10, but is not limited to this as long as the purpose of the present invention is achieved. No.

The breathable film is not particularly limited, but may be a breathable film made of polyolefin resin, and preferably a breathable polyethylene film.

The nonwoven fabric is not particularly limited, but may be made of one or more materials selected from, for example, polypropylene, polyester, polyethylene, polyterephthalate, nylon, and aramid.

The composite sheet of the present invention may have antistatic properties of 2.8×10 ¹⁰ Ω or less or 2.8×10 ⁹ Ω or less according to EN1149-1, and is not necessarily limited thereto, but satisfies the above range to provide excellent and permanent antistatic properties. It is preferred because it has .

Another aspect of the present invention is to provide an antistatic composition containing chitosan having an ionic group and an organic binder.

Chitosan having the ionic group may be chitosan substituted with a quaternary ammonium group.

By including chitosan having the ionic group, the antistatic composition not only has excellent antistatic properties, but, unlike materials used in existing antistatic compositions, its properties are maintained over time.

The organic binder is not particularly limited, but includes polyvinyl acetate, polycarbonate, polyacrylate, polybutylate, polyether, polyester, polyurethane, polyacrylic-urethane copolymer, vinyl acetate-vinyl alcohol-vinyl chloride copolymer. It may be any one or more components selected from coalescence, etc.

The antistatic composition may further include a conductive material, and is not particularly limited as long as it is a conductive material, for example, conductive materials such as conductive polymers, conductive metal particles, carbon black, graphite, and carbon nanofibers. There may be one or more than one selected from .

The conductive polymer is not particularly limited, but for example, polyaniline, polypyrrole, polythiophene, poly(3,4-ethylenethiophene), or derivatives thereof may be used.

The conductive metal particles are not particularly limited as long as they are conductive metal particles, but for example, single particles such as copper, nickel, zinc, brass, gold, silver, etc., or mixtures of copper, nickel, zinc, brass, etc. It may be a particle whose surface has been treated with metal. The average particle diameter may be 0.001 ㎛ to 100 ㎛.

The carbon black may be natural carbon black or artificial carbon black, and its particle size may be 0.01 ㎛ to 100 ㎛ or 0.1 ㎛ to 50 ㎛.

The chitosan having the ionic group may be included in an amount of 0.1 wt% to 10 wt%, 0.5 wt% to 5 wt%, or 1 wt% to 3 wt%, based on the weight of the entire antistatic composition including the solvent. The organic binder may be included in the range of 0.1 wt% to 30 wt%, preferably 1 wt% to 25 wt%, or 5 wt% to 20 wt%, based on the weight of the total composition, but is limited to this as long as the purpose of the present invention is achieved. I never do that.

Additionally, the conductive material may be included in an amount of 0.5 wt% to 10 wt%, 1 wt% to 8 wt%, or 2 wt% to 5 wt% based on the total weight of the antistatic composition.

The remaining content of the antistatic composition may be a solvent, and the solvent is not limited thereto, but is propylene glycol monomethyl ether acetate, toluene, ethyl acetate, butyl acetate, acetone, methanol, butyl carbitol, butyl carbitol acetate, butyl It may be one or more selected from the group consisting of cellosolve, butyl cellosolve acetate, terpineol, and water.

In one aspect of the present invention, the weight ratio of chitosan having an ionic group and the conductive material may be 1:0.05 to 1:50 or 1:0.1 to 1:10, but is not limited to this as long as the purpose of the present invention is achieved. No.

Another aspect of the present invention is to provide any one of clothing selected from protective clothing, anti-static clothing, sports clothing, work clothing, chemical clothing, dustproof clothing, and pest control clothing made from the composite sheet.

Various clothing made from the composite sheet has excellent flexibility and is comfortable to wear, has excellent antistatic properties, and maintains the properties.

Hereinafter, embodiments of the present invention will be described in detail below. However, the examples described below only illustrate a part of the present invention, and the present invention is not limited thereto.

Hereinafter, the antistatic properties of the composite sheet were measured according to EN1149-1.

<Manufacturing Example 1>

45 g of chitosan was dispersed in a mixed solvent of 50 mL of water and 300 mL of acetone and then swelled at 50°C for 2 hours to obtain a chitosan solution. 75 g of a 60 wt% glycidyl trimethyl ammonium chloride aqueous solution was slowly added to the chitosan solution, and then 0.5 g of caustic soda was added as a catalyst and reacted at 70° C. for 5 hours.

The reacted mixture was filtered, washed three times with an 80 wt% aqueous acetone solution, and dried to prepare chitosan substituted with a quaternary ammonium group. The prepared quaternary ammonium chitosan had a degree of substitution of 72% and a yield of 85%, and when it was dissolved in an aqueous solution at 1.0 wt%, the insoluble matter was 0.1%.

<Example 1>

1) Manufacturing of a laminated sheet made of non-woven fabric and breathable film

A breathable film was prepared by mixing 50 parts by weight of calcium carbonate (Yabashi Korea YK1C) with 100 parts by weight of low-density polyethylene (Hanwha Chemical, HANWHA LDPE 955, MI: 7.5, density: 0.913), melt-extruding and stretching, and the basis weight was 20. g/m2, water vapor permeability was 3,500 g/m2·24hr, air permeability was 520 sec in terms of Gurley constant, and water pressure was 62 cm/H ₂ O.

The prepared breathable film was introduced into an adhesive application device and an adhesive (Samho Chemical Co., Ltd., SPU-7385) was applied using a coating roller. At this time, the application roller used a gravure coater copper plate of 210 mesh laser engraved in a grid pattern for transfer application.

The breathable film to which the adhesive is applied is transferred to a lamination device together with polyethylene spunbond nonwoven fabric (basis weight 25 g/m2) and supplied to one side of the breathable film, and are pressed and bonded to each other at 175°C by a compression roller to form a breathable material for the nonwoven fabric. A laminated sheet with laminated films was manufactured.

2) Preparation of antistatic composition

A carbon black dispersion was prepared by dispersing 20 g of carbon black (average particle diameter 200 nm) in 10 g of propylene glycol monomethyl ether and 20 g of ethyl acetate.

In addition, 5 g of chitosan substituted with a quaternary ammonium group of Preparation Example 1 and 30 g of vinyl acetate-vinyl alcohol-vinyl chloride copolymer (Suzhou Direction Chemical Co., Ltd., VAGD) as a binder were dissolved in 15 g of methyl ethyl ketone to prepare chitosan. A mixed solution was prepared.

An antistatic composition was prepared by mixing the carbon black dispersion and chitosan mixed solution in a high speed impeller mixer for more than 30 minutes until no particles (sand) were observed.

3) Manufacturing of anti-static composite sheets

A composite sheet was prepared by applying the antistatic composition prepared above to the surface of the polyethylene breathable film of the prepared laminated sheet and then aging it at 60° C. for 12 hours. The thickness of the coating layer prepared by the above method was 0.5 ㎛. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

<Example 2>

The same procedure as Example 1 was performed except that the antistatic composition prepared in Example 1 was applied to the surface of the nonwoven fabric of the laminated sheet prepared above. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

<Example 3>

0.5 g of poly(3,4-ethylenedioxythiophene) (PEDOT), 87.5 g of ethanol, 5 g of chitosan substituted with quaternary ammonium group of Preparation Example 1, polyurethane dispersion (tricompatibility, SPU-7835 solid content 35 wt%) The same procedure as Example 1 was carried out, except that an antistatic composition prepared by mixing 5 g of a wetting agent (Merck, Tivida FL 2300, fluorine-based surfactant) and 2 g was applied. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

<Example 4>

The same procedure as Example 3 was carried out, except that the antistatic composition prepared in Example 3 was applied to the surface of the nonwoven fabric in the laminated sheet prepared above. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

<Comparative Example 1>

0.45 g of self-aligned multi-walled carbon nanotubes, acrylate, with an average length of 10 mm, an average diameter of 3 nm, and an apparent density of 0.015 g/cm ² were placed on a stirrer in a 5 L container. A first dispersion was prepared by mixing 0.9 g of dispersant (density: 1.02 g/cm ³ at 20°C), 69.25 g of ethanol, and 29.4 g of distilled water and stirring it at 2,500 rpm for 10 hours using a bead mill.

14 g of the prepared primary dispersion, 28.5 g of ethanol, 39.5 g of distilled water, 8 g of water-soluble polyurethane (SD-22HG), and 10 g of N-methyl pyrrolidone were mixed using a bead mill at 100 rpm for 1 hour. By further stirring, an antistatic composition was prepared.

The same procedure as Example 1 was performed, except that the antistatic composition prepared in Comparative Example 1 was used instead of the antistatic composition of Example 1. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

<Comparative Example 2>

The same procedure as Example 1 was performed except that unmodified chitosan was used instead of the modified chitosan prepared in Preparation Example 1. The sheet resistance of the manufactured composite sheet was measured and shown in Table 1.

Evaluation results Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Initial sheet resistance (Ω) 2.8×10 ⁵ 2.8×10 ⁸ 2.8×10 ⁷ 2.8×10 ⁹ 2.8×10 ¹⁰ 2.8×10 ⁹ 1 week later
Sheet resistance (Ω) 2.8×10 ⁵ 2.8×10 ⁸ 2.8×10 ⁷ 2.8×10 ⁹ 2.8×10 ¹¹ 2.8×10 ¹³ 1 month later
Sheet resistance (Ω) 2.8×10 ⁵ 2.8×10 ⁸ 2.8×10 ⁷ 2.8×10 ⁹ 2.8×10 ¹³ -

The sheet resistance of the composite sheets manufactured in Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were measured for initial sheet resistance, sheet resistance after 1 week, and sheet resistance after 1 month, and are shown in the table.

As a result, the composite sheets according to Comparative Examples 1 and 2 that did not use chitosan substituted with quaternary ammonium groups not only had high initial sheet resistance, but also rapidly increased sheet resistance over time, making them unsuitable for use as antistatic purposes. did.

On the other hand, in the case of Examples 1 and 2 containing chitosan and carbon black substituted with quaternary ammonium groups prepared in Preparation Example 1, the sheet resistance was maintained until one month later, showing that it had a permanent antistatic effect. In addition, in the case of Examples 3 and 4 containing the substituted chitosan of Preparation Example 1 and poly(3,4-ethylenedioxythiophene) (PEDOT) as the conductive polymer, the sheet resistance was also maintained until 1 month, providing permanent anti-static properties. It was found to be effective. It was found that clothing manufactured using this is suitable for use in protective clothing, antistatic clothing, sports clothing, work clothing, chemical clothing, dustproof clothing, and pest control clothing that require antistatic effects.

Claims (16)

An antistatic layer formed by applying an antistatic composition containing chitosan having an ionic group, a conductive material, and an organic binder on one or both sides of a laminated sheet of nonwoven fabric and a breathable film, wherein the conductive material is a conductive polymer and carbon black. , graphite, and carbon nanofibers, or one or more composite sheets.
According to clause 1,
A composite sheet wherein the chitosan having an ionic group in the antistatic composition is chitosan substituted with a quaternary ammonium group.
delete delete According to clause 1,
The antistatic composition is a composite comprising 0.1 wt% to 10 wt% of chitosan having an ionic group, 0.1 wt% to 30 wt% of an organic binder, and 0.5 wt% to 10 wt% of a conductive material relative to the weight of the entire composition. Sheet.
According to clause 1,
A composite sheet wherein the weight ratio of chitosan having an ionic group and the conductive material is 1:0.05 to 1:50.
According to clause 1,
A composite sheet wherein the breathable film is a polyolefin-based breathable film.
According to clause 1,
The nonwoven fabric is a composite sheet made of one or more materials selected from polypropylene, polyester, polyethylene, and copolymers thereof.
According to clause 1,
Composite sheet with anti-static properties of 2.8×10 ¹⁰ Ω or less according to EN1149-1.
An antistatic composition comprising chitosan having an ionic group, a conductive material, and an organic binder, wherein the conductive material is one or more selected from conductive polymers, carbon black, graphite, and carbon nanofibers.
According to clause 10,
An antistatic composition wherein the chitosan having the ionic group is chitosan substituted with a quaternary ammonium group.
delete delete According to clause 10,
An antistatic composition comprising 0.1 wt% to 10 wt% of chitosan having an ionic group, 0.1 wt% to 30 wt% of an organic binder, and 0.5 wt% to 10 wt% of a conductive material, based on the weight of the entire composition.
According to clause 10,
An antistatic composition wherein the weight ratio of chitosan having an ionic group and the conductive material is 1:0.05 to 1:50.
Any one selected from protective clothing, anti-static clothing, sports clothing, work clothing, chemical clothing, dust-proof clothing, and pest control clothing manufactured from the composite sheet of any one of claims 1, 2, and 5 to 9. clothing.