KR101099830B1 - Antistatic composition for inside addition and products comprising thereof - Google Patents

Abstract

The present invention relates to an internal antistatic composition and an antistatic product comprising the same. Specifically, the internal antistatic composition of the present invention comprises 0.1 to 10 parts by weight of an ionic liquid; 1 to 60 parts by weight of carbon nanotubes; 0.1 to 5 parts by weight of at least one additive selected from the group consisting of a heat stabilizer, a plasticizer, an ultraviolet stabilizer, and a dispersant; And 30 to 90 parts by weight of the thermoplastic polymer. In addition, the antistatic composition may be mixed with the polymer resin to prepare an antistatic product having excellent antistatic effect and excellent stretchability, heat resistance and weather resistance.

Internal Type, Antistatic Agent, Ionic Liquid, Carbon Nanotube

Description

Internal antistatic composition and antistatic product comprising same

The present invention relates to an internal antistatic composition and an antistatic product comprising the same, and specifically, to an antistatic product having excellent heat resistance and stretchability and low surface resistance without deteriorating the physical properties of the polymer when added to the polymer resin. It relates to an internal antistatic composition and an antistatic product comprising the same.

In recent years, as the export of electronic components, semiconductor products and medical devices has increased, the demand for antistatic products has gradually increased. In general, plastic products processed from polymer resins have a surface resistance in the range of 10 ¹⁵ to 10 ¹⁸ Ω, making it easy to attach contaminants due to the generation of static electricity. In order to prevent this, the surface resistance value should be kept below 10 ¹⁰ 인, which is an antistatic property, and the surface resistance value should be lower in order to be used in packaging films and conductive paints such as semiconductors, medical devices and ultra-precision parts.

As the antistatic agent, an antistatic agent of a surface coating antistatic agent used by coating an antistatic agent on an insulator base plastic surface and an antistatic agent prepared by mixing an antistatic agent in the manufacture of the base plastic is widely used.

Since the antistatic agent for surface coating manufactures an antistatic film and sheet using various coating methods on the base plastic, not only the productivity is excellent, but also the surface resistance according to the control of physical properties of the antistatic coating liquid (10 ² ~ 10 ¹⁰ Ω). / sq) has the advantage of being able to adjust freely. However, not only the permanent antistatic effect is inadequate, there is a problem that the durability of the antistatic agent is not maintained.

On the contrary, the internal antistatic agent for adding and mixing the antistatic agent to the base plastic, which is an insulator, can be used together with other additives in plastic molding, so that the operation is simple and the durability can be maintained even after molding. However, the conventional antistatic agent for internal additives has a problem in thermal stability at high temperature such as decomposition and evaporation at 150-200 ° C., which is a plastic molding temperature, in a process of adding a certain concentration to the polymer resin before molding and undergoing mechanical mixing. In addition, carbon black has problems such as deterioration of polymer properties and dust generation according to the added amount.

An object of the present invention to solve the above problems is an addition-type antistatic composition which can prepare an antistatic product with excellent surface resistance, heat resistance and stretchability and low surface resistance without deteriorating the physical properties of the polymer when added to the polymer resin and It is to provide an antistatic product comprising the same.

The present invention to achieve the above object,

Per 100 parts by weight of the total composition

0.1 to 10 parts by weight of the ionic liquid;

1 to 60 parts by weight of carbon nanotubes;

0.1 to 5 parts by weight of at least one additive selected from the group consisting of a heat stabilizer, a plasticizer, an ultraviolet stabilizer, and a dispersant; And

It provides an internal antistatic composition comprising 30 to 90 parts by weight of the thermoplastic polymer.

The thermoplastic polymer is polyester (PET A, PET G, PET G-PET A-PET G triplet), polystyrene, polyimide, polyamide, polysulfonate, polycarbonate, polyacrylate, polyvinyl acetal, poly Methyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, modified polyphenylene oxide (MPPO), SBS, Styrene-Acrylonitrile (SAN), synthetic rubber, phenol resin, epoxy resin, acrylic resin, urethane It may be a single or a mixture thereof selected from the group consisting of resins, ABS resins and blends or copolymers thereof.

The carbon nanotubes may have a length of 1 to 60 μm and a diameter of 0.1 to 50 nm.

The cations of the ionic liquid are ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, pyridazinium ), Pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolinium, thriazolium, triazolium and guanidinium It can be selected from the group.

The anion of the ionic liquid can be selected from the group consisting of halogen, sulfate, sulfonate, amide, imide, borate, phosphate, antimonate, decanate and cobalt tetra-carbonyl.

In order to achieve the other object of the present invention,

It provides an antistatic type product prepared by mixing the internal additive-type antistatic composition to 10 to 60 parts by weight based on the polymer resin.

In the mixing process, the compatibilizer may be included in an amount of 0.1 to 5 parts by weight based on the polymer resin.

The product may be a sheet, a film.

On one side of the antistatic product

Per 100 parts by weight of the total composition

5 to 30 parts by weight of the curable binder;

0.1 to 15 parts by weight of carbon nanotubes;

0.1 to 5 parts by weight of at least one additive selected from the group consisting of dispersants, slip agents, flow improvers, antiblocking agents and ultraviolet stabilizers; And

An antistatic coating composition comprising 30 to 90 parts by weight of an organic solvent may be coated.

The curable binder may be a heat curable or photocurable binder.

The thermosetting binder may be a single or a mixture of acrylic resins, urethane resins, urethane-acrylic copolymers, ester resins, ether resins, amide resins, epoxy resins, and melamine resins.

The photocurable binder may be acrylic, urethane, urethane-acrylic mono or oligomer.

The internal antistatic composition of the present invention can be used together with other additives in the processing of plastics, which not only makes the operation simple, but also retains durability after molding.

The internal antistatic composition of the present invention does not lower the physical properties of the polymer resin itself even when added to the polymer resin.

Products such as films or sheets made of the internally-loaded antistatic composition of the present invention have low surface resistance and are excellent in antistatic effects.

The product made of the additive-resistant antistatic composition of the present invention is excellent in stretchability and heat resistance and can be used as various electronic components.

The product made of the antistatic composition of the present invention has excellent weather resistance and does not rapidly decrease surface resistance even when exposed to ultraviolet light.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

The present invention is an ionic liquid; Carbon nanotubes; At least one additive selected from the group consisting of thermal stabilizers, plasticizers, ultraviolet stabilizers and dispersants; And it provides an internal antistatic composition comprising a thermoplastic polymer. The anti-static type antistatic composition may be mixed with other additives and the like with a polymer resin to facilitate the operation and to produce an antistatic product having excellent antistatic effect with low surface resistance while having excellent weather resistance, heat resistance and stretchability.

The ionic liquid is an ionic salt having the property of being present as a liquid at temperatures of up to 100 ° C. In particular, the ionic liquid present as a liquid at room temperature is referred to as room temperature ionic liquid (RTIL). Since ionic liquids are non-volatile, they have no vapor pressure, have high ionic conductivity, and evaporate at high temperatures above 300 ° C. The ionic liquid serves to improve the heat resistance of the antistatic product.

The ionic liquid is composed of a cation and an anion, and the unique physical and chemical properties of the ionic liquid are greatly influenced by the structure of the cation and anion of the ionic liquid and can be optimized according to the user's purpose of use. The cation of the ionic liquid may be used without limitation, those known in the art, preferably ammonium, imidazolium, oxazolium, piperidinium, pyrazinium (pyrazinium), pyrazolium, pyridazinium, pyridinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrialinium, thriazolium It may be selected from the group consisting of triazolium (triazolium) and guanidinium (guanidinium). Specifically, cations represented by any one of the following Chemical Formulas 1 to 20 may be used:

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

(In Chemical Formulas 1 to 20,

R ₁ to R ₆ Is independently an alkyl or phenyl group having 1 to 9;

The anion of the ionic liquid may be used without limitation as is known in the art, but preferably halogen, sulfate, sulfonate, amide, imide, borate, phosphate, antimonate, decanate and cobalt tetra-carbonyl It can be selected from the group consisting of. Particular examples of the ^{anion, F -, Cl -, Br} -, I -, NO 3 -, N (CN) 2 -, ClO 4 -, RSO 3 - ( where R is an alkyl group or a C 1 to 9 a phenyl group), RCOO ^- (, where R is an alkyl group or a phenyl group) C 1 to _{^{9, PF6 -, (CF 3}} ) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 - ^{_{, (CF 3) 5 PF -}} , (CF 3) 6 P -, (CF 3 SO 3 -) 2, (CF 2 CF 2 SO 3 -) 2, (C n F 2n +1 SO 2) 2 N - (where n is 1 to _{4), CF 3 CF 2 (} CF 3) 2 CO-, (CF 3 SO 2) 2 CH-, BF 4 -, bis oxide borate Salto (bis oxalto borate, BOB), fluorine oxide Salto Borate (fluoro oxalto borate, FOB), tetra fluoro borate, hexafluoro phosphate, bis (trifluoromethylsulfonyl), imidate, perchloric acid, tris (trifluoromethylsulfonyl) carbonate, trifluoro Methanesulfonate, trifluoroacetate, organic carboxylic acid, and the like.

The ionic liquid may be included in an amount of 0.1 to 10 parts by weight based on the internal antistatic composition. When included in less than 0.1 parts by weight may increase the surface resistance of the product using the internal antistatic composition of the present invention, when included in more than 10 parts by weight may result in a transition phenomenon and may reduce the compatibility.

The carbon nanotube is a tube-shaped molecule formed by roundly rolling a graphite plate formed by connecting hexagonal rings composed of six carbons to each other. Since the carbon nanotubes have excellent rigidity and electrical conductivity, the film hardness increases and the antistatic function is improved. In addition, since it does not decompose upon exposure to ultraviolet rays or heat, weather resistance is increased compared with the case of using a conductive polymer.

The carbon nanotubes may be prepared by methods known in the art, such as chemical vapor deposition, arc discharge, plasma torch, and ion bombardment, and are not limited thereto. The carbon nanotubes may be a single-walled carbon nanotube (SWNT) having a single-wall structure or a multi-walled carbon nanotube (MWNT) having a multi-walled structure. It is not limited. Various carbon nanotubes can be used, such as chiral, zigzag, and armchair. In addition, the carbon nanotubes may be subjected to a pretreatment step by a conventional method known in the art, but may not be subjected to the pretreatment step.

The carbon nanotubes preferably have a length of 1 to 60 μm and a diameter of 0.1 to 50 nm. It is excellent in transparency or dispersibility within the said range.

The carbon nanotubes may be included in an amount of 1 to 60 parts by weight. If it is included in less than 1 part by weight may increase the surface resistance of the antistatic product, the effect of improving weather resistance is insignificant, when included in more than 60 parts by weight may not be good dispersibility, when added to the polymer resin polymer resin Can lower the physical properties.

The additives include at least one selected from the group consisting of thermal stabilizers, plasticizers, ultraviolet stabilizers and dispersants.

The UV stabilizer improves the weather resistance of the antistatic product and serves to reduce yellowing caused by the effect of ultraviolet rays. The UV stabilizer may include a benzophenol-based or benzotriazole-based.

The heat stabilizer serves to reduce the decomposition at high temperatures of the internally charged antistatic composition, and those known in the art can be used without limitation.

The plasticizer may be used without limitation to those known in the art to increase thermoplasticity when mixed with a polymer resin, and specifically, dioctylphthalate (DOP), dioctyl adipate (DOA) or tricresyl phosphate (TCP). ).

The dispersant may be used without limitation to those known in the art to improve the dispersibility of the carbon nanotubes, preferably a high molecular anionic surfactant, low molecular unsaturated carboxylic acid, or polysiloxane copolymer, unsaturated polyamine amide salt , Polyethylene glycol, ethyl cell solution and the like can be used.

The additive may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the internal antistatic composition. If the content is less than 0.1 part by weight, the effect of adding the additive is insignificant. If the content is more than 5 parts by weight, the physical properties of the polymer resin may be reduced.

The thermoplastic polymer may be uniformly mixed with the ionic liquid, carbon nanotubes, and additives, and serves to improve compatibility with the polymer resin when preparing an antistatic product. The thermoplastic polymer may be used without limitation, those known in the art, specifically, polyester (triple of PET A, PET G, PET G-PET A-PET G), styrene-butadiene copolymer, polystyrene, poly Mid, polyamide, polysulfonate, polycarbonate, polyacrylate, polyvinyl acetal, polymethyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, modified polyphenylene oxide (MPPO), SBS And selected from the group consisting of Styrene-Acrylonitrile (SAN), synthetic rubber, phenol resin, epoxy resin, acrylic resin, urethane resin, ABS resin, and blends or copolymers thereof. The thermoplastic polymer may be included in an amount of 30 to 90 parts by weight based on 100 parts by weight of the total composition. When included in less than 30 parts by weight may reduce the compatibility with the polymer resin in the production of antistatic products, may not be properly mixed with ionic liquids, carbon nanotubes and additives, including more than 90 parts by weight When the content of ionic liquids and carbon nanotubes is relatively reduced, heat resistance and antistatic effect may be reduced.

The present invention provides an antistatic product which is prepared by mixing the internal additive-type antistatic composition into a polymer resin. The antistatic type product has a small surface resistance and is excellent in antistatic effect, as well as excellent in stretchability, heat resistance and weather resistance.

The internally-loaded antistatic composition may be included in an amount of 10 to 60 parts by weight based on the polymer resin. If it is included in less than 10 parts by weight, the antistatic effect is insignificant. If it is included in more than 60 parts by weight, the physical properties of the polymer resin itself may be reduced.

The polymer resin is not limited as long as it can be applied to the internal antistatic composition. Various thermoplastic resins are possible, including reactive thermosetting resins. Specifically, acrylonitrile rubber, fluorine rubber, silicone rubber, ethylene propylene rubber, urethane rubber, chloroprene rubber, styrene butadiene rubber, butyl rubber, chlorosulfonate propylene rubber, polymer sulfide rubber, acrylate rubber, epi Synthetic rubbers such as crolidrin rubber and acrylonitrile ethylene rubber; Thermoset polyurethanes; Thermoplastic polyurethane (TPU); Polyvinyl chloride (PVC); Polyvinyl alcohol; Polyvinyl acetal; ABS; SBS; Polycarbonate; Polypropylene; Polyethylene; polystyrene; nylon; And it may be a single or a mixture thereof selected from the group consisting of polyester. In addition, the polymer resin may be formed in a single layer or multiple layers.

A compatibilizer may be further included in the mixing process. The compatibilizer serves to increase the miscibility of the internal additive type antistatic composition and the polymer resin. The compatibilizer is an olefin polymer, an olefin copolymer (ethylene-propylene block copolymer), a polystyrene grafted or copolymerized maleic acid, a polymer including an acrylic group (polymethyl methacrylate, poly (styrene-acrylonitrile), ABS Etc.), styrene-ethylene-butylene-styrene tetrapolymer, styrene-ethylene-butylene-styrene tetrapolymer grafted with maleic acid, styrene-butadiene-styrene terpolymer and styrene-isobutylene-styrene terpolymer It may be a single or a mixture thereof selected from the group consisting of. The compatibilizer may be included in an amount of 0.1 to 5 parts by weight based on the polymer resin. The inclusion of less than 0.1 parts by weight reduces the compatibility, and the inclusion of more than 5 parts by weight increases the surface resistance of the antistatic product.

The antistatic product is not limited as long as it can be produced by mixing the internal additive-type antistatic composition into a polymer resin, but may be specifically an antistatic sheet, a film, a laminated support for display glass and the like. The internal antistatic composition may be mixed with a polymer resin and injected at a predetermined temperature to prepare a desired antistatic product. In addition, the antistatic sheet or the film may be vacuum molded to produce an antistatic tray for an electronic component for an electronic component.

The antistatic coating composition may be coated on at least one surface of the antistatic product to form an antistatic coating layer. An antistatic coating layer may be formed on one surface of the antistatic product to further increase the antistatic effect.

The antistatic coating composition is a curable binder; Carbon nanotubes; At least one additive selected from the group consisting of dispersants, slip agents, flow improvers, antiblocking agents and ultraviolet stabilizers; And organic solvents.

The curable binder may be a heat curable or photocurable binder. The thermosetting binder may be used in the art without limitation, specifically, acrylic resins, urethane resins, urethane-acrylic copolymers, ester resins, ether resins, amide resins, epoxy resins, and melamine resins. It may be a single or a mixture thereof selected from the group consisting of. The photocurable binder may be acrylic, urethane, urethane-acrylic mono or oligomer, but is not limited thereto. The curable binder may be included in an amount of 5 to 30 parts by weight based on 100 parts by weight of the total composition. When the curable binder is included in less than 5 parts by weight, the adhesion, wear resistance and scratch resistance may be reduced, and when included in more than 30 parts by weight may increase the surface resistance to reduce the antistatic effect.

Since the carbon nanotubes are the same as described above, description thereof will be omitted. The carbon nanotubes may be included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the total composition. When the carbon nanotubes are included in less than 0.1 parts by weight, the surface resistance may increase to reduce the antistatic effect, and when included in excess of 15 parts by weight may result in a decrease in physical properties such as permeability, wear resistance and scratch resistance.

The additive may be at least one selected from the group consisting of a dispersant, a slip agent, a flow improver, an antiblocking agent and an ultraviolet stabilizer. As the slip agent, a silicon-based material may be used, and specifically, a siloxane copolymer, a modified polysiloxane, or the like may be used. As the antiblocking agent, PMMA, PS, or silicon beads may be used. The additive may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. When the amount is less than 0.1 part by weight, the effect of the addition of the additive is insignificant, and when it exceeds 5 parts by weight, the physical properties of the polymer resin may be lowered.

The organic solvent may be used without limitation as long as it is capable of dissolving and dispersing the curable binder, carbon nanotubes, and additives. Specifically, the organic solvent is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NMP), ethylene glycol, propylene glycol methyl ether, 2-butanone, 4-methyl- 2-pentanone, ethyl cellosolve, methyl cellosolve, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol and di-acetone alcohol It is possible to use alone or mixtures thereof. In addition, the organic solvent may be used by mixing with water. The organic solvent may be included in an amount of 50 to 90 parts by weight based on 100 parts by weight of the total composition. When included in an amount of 50 to 90 parts by weight, the curable binder, carbon nanotubes and additives are uniformly dissolved and do not affect other physical properties.

Looking at the coating method in detail, the antistatic coating composition on at least one surface of the antistatic product in the manner of gravure coating, comma coating, roll coating, bar coating, dip coating, flow coating, spray coating, slot die, etc. After coating, heat drying at a temperature in the range of 40 to 150 ° C. for 1 to 10 minutes to completely remove the organic solvent in the coating composition, followed by heat curing, or after the heat drying, irradiating and curing UV light having a light amount of 250 to 1,000 mJ / cm 3 Curing may form an antistatic coating layer.

The antistatic tray may be manufactured by vacuum forming the antistatic coating layer formed on at least one surface of the antistatic product prepared by mixing the internally-type antistatic composition with the polymer resin as described above.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. This is for the purpose of illustrating the present invention, and thus the scope of the present invention is not limited thereto.

< Example  1> Internal  Preparation of Antistatic Composition

30% by weight of carbon nanotubes (multi-layer carbon nanotubes), 5% by weight of ionic liquid [1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide)], thermal stabilizer (inorganic materials, CWT-83, CWT Co.) 1% by weight, polyester amide-based resin 64% by weight in a blender for 5 minutes, using a twin screw extruder barrel 1, barrel 2 extrusion temperature is 170 ℃, extrusion speed 200rpm Extrusion to prepare an internal antistatic composition.

< Example  2> Manufacture of antistatic sheet

20 to 100% by weight of the internal antistatic composition prepared in Example 1, 77% by weight of polystyrene (PS), a universal thermoplastic polymer resin, 3% by weight of a compatibilizer [poly (styrene-acrylonitrile)] by mixing 150 ~ 180 An extrusion rate was extruded at a temperature of 200rpm to prepare an antistatic sheet.

< Example  3> Manufacture of antistatic tray

The antistatic sheet prepared in Example 2 was vacuum molded at a temperature of 150 to 180 ° C., thereby preparing an antistatic tray that was three times stretched.

< Example  4> Formation of Antistatic Sheet

4-1. Acrylic light-curable binder (Dipentaerythritol hexaacrylate 10% by weight, Pentaerythritol triacrylate 5% by weight), carbon nanotube (length 30㎛, diameter 10nm, multi-wall) 1% by weight, light curing agent (Igacure 184, Ciba Geigy Co. 1% by weight, a slip agent (Tego glide 450, Tego Co.) 0.5% by weight, an organic solvent (40% by weight of isopropyl alcohol, 82.5% by weight of ethylene glycol) was added to prepare an antistatic coating composition.

4-2. The antistatic coating composition was coated on the antistatic sheet prepared in Example 2 by a gravure coating method, and thermally cured and dried at 60 ° C. for 1 minute to remove the solvent in the coating composition, and then irradiated with ultraviolet light of 500 mJ / cm 3. An antistatic sheet was prepared.

< Example  5> Manufacture of antistatic sheet

5-1. 1% by weight of carbon nanotubes (multi-wall of 30 μm in length, 10 nm in width), 15% by weight of acrylic copolymer binder (Carboset CR780, BFGoodrich Co.), 50% by weight of isopropyl alcohol, 32% by weight of methylcellulose solution, dispersant 1% by weight (polymer anionic, HPA-328, Yeungsan Co.) and 1% by weight of a flow improver (HPA-538, Yeungsan Co.) were combined to prepare a thermosetting antistatic coating composition.

5-2. The heat curable antistatic coating composition was coated on the antistatic sheet prepared in Example 2 by a gravure coating method, followed by thermal curing drying at a temperature of 60 to 80 ° C. for 1 minute to remove the solvent in the coating composition, followed by heat curing Sheets were prepared.

< Example  6> Manufacture of antistatic tray

The antistatic sheet prepared in Example 5 was vacuum molded at a temperature of 150 to 180 ° C. to prepare an antistatic tray that was three times stretched.

< Comparative example  1> Preparation of antistatic sheet

1-1. An internal antistatic composition was prepared in the same manner as in Example 1, except that 35 wt% of carbon nanotubes were used without using an ionic liquid.

1-2. An antistatic sheet was prepared in the same manner as in Example 2 using the internally-loaded antistatic composition prepared in 1-1.

< Comparative example  2> Manufacture of antistatic sheet

2-1. An internal antistatic composition was prepared in the same manner as in Example 1, except that 35 wt% of the ionic liquid alone was used without using carbon nanotubes in Example 1.

2-2. An antistatic sheet was prepared in the same manner as in Example 2 using the internally-loaded antistatic composition prepared in 2-1.

< Comparative example  3> Manufacture of antistatic sheet

3-1. An internal antistatic composition was prepared in the same manner as in Example 1 except for using the surfactant (Superfloc C-591, Cytec) instead of the ionic liquid in Example 1.

3-2. An antistatic sheet was prepared in the same manner as in Example 2 using the internally-loaded antistatic composition prepared in 3-1.

< Experimental Example  1> Measurement of surface resistance

The surface resistance of the sheets or trays prepared in Examples 2 to 6 and Comparative Examples 1 to 3 was measured under a condition of 55% RH, 23 ° C., and an applied voltage of 500V according to ASTM D257. The results are shown in Table 1 below.

Example 2 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface resistance
(Ω / ㎠) 10 ⁵ 10 ⁴ 10 ³ 10 ⁶ 10 ⁸ 10 ⁶ After 5 times extension
Surface resistance
(Ω / ㎠) 10 ⁷ 10 ⁷ 10 ^{4 ~ 5} 10 ¹¹ 10 ¹² 10 ¹¹

As shown in Table 1, it can be seen that the sheet produced using the internally-loaded antistatic composition of the present invention has a smaller surface resistance than the comparative example, and thus has an excellent antistatic effect. In addition, even when stretched 5 times, the increase rate of the surface resistance is lower than that of the comparative example, it can be seen that the excellent stretchability. In the case of the sheet of Examples 4 to 5 in which the coating layer was formed on the sheet prepared by mixing the internal antistatic composition, the surface resistance is lower than that of the sheet of Example 2, so that the antistatic agent is combined with the antistatic agent and the antistatic coating agent. It can be seen that the effect is excellent.

< Experimental Example  2> weather resistance test

The weather resistance test was conducted at 40 ° C. for 12 hours at a strength of 500 W / m 2 at 280 nm using a WeatherOmeter, and then the degree of yellowing and surface resistance were measured. The results are shown in Table 2 below.

Example 2 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Yellowing phenomenon none none none none has exist has exist Surface resistance
(Ω / sq) Early 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³ 1 x 10 ⁶ 1 × 10 ⁸ 5 × 10 ⁶ After the test 2 × 10 ⁴ 2 × 10 ⁶ 5 × 10 ⁴ 1 × 10 ⁷ 8 × 10 ¹² 7 × 10 ⁸

As shown in Table 2, in the case of the sheet prepared using the antistatic coating composition of the present invention, yellowing was not observed, and it can be seen that weather resistance is excellent. This may be because carbon nanotubes do not decompose even when exposed to ultraviolet light. Thus, the sheet of Comparative Example 1 containing only carbon nanotubes did not exhibit yellowing, and even after weathering test, the increase rate of surface resistance was not greater than that of other comparative examples.

< Experimental Example  3> heat / moisture resistance test

The sheets prepared in Examples and Comparative Examples were left in a constant temperature and humidity chamber at a temperature of 70 ° C. and a humidity of 90% for 72 hours, and then the surface resistance was measured. The results are shown in Table 3 below.

Example 2 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Surface resistance
(Ω / sq) Early 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³ 1 x 10 ⁶ 1 × 10 ⁸ 1 x 10 ⁶ After the test 1 × 10 ⁵ 1 × 10 ⁴ 1 × 10 ³ 1 × 10 ⁷ 1 × 10 ⁹ 1 × 10 ¹⁰

As shown in Table 3, in the case of the sheet prepared using the internally-loaded antistatic composition of the present invention, even after 72 hours at a temperature of 70 ° C. and a humidity of 90%, there was no change in the surface resistance.

As described above, since the additive-resistant antistatic composition of the present invention can be mixed with other additives to the polymer resin, the workability is simple, and the stretchable, heat resistance and weather resistance are excellent by using the additive-resistant antistatic composition. Antistatic products can be prepared.

Claims (14)

Per 100 parts by weight of the total composition 0.1 to 10 parts by weight of the ionic liquid; 1 to 60 parts by weight of carbon nanotubes; 0.1 to 5 parts by weight of at least one additive selected from the group consisting of a heat stabilizer, a plasticizer, an ultraviolet stabilizer, and a dispersant; And Internal antistatic composition comprising 30 to 90 parts by weight of the thermoplastic polymer. The method of claim 1, The thermoplastic polymer is polyester, polystyrene, polyimide, polyamide, polysulfonate, polycarbonate, polyacrylate, polyvinyl acetal, polymethyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, modified polyphenylene oxide , SBS, SAN, synthetic rubber, phenolic resin, epoxy resin, acrylic resin, urethane resin, ABS resin and blends or copolymers thereof selected from the group consisting of a single or a mixture thereof. The method of claim 1, The carbon nanotubes are 1 to 60㎛ in length, internal diameter antistatic composition, characterized in that 0.1 to 50nm in diameter. The method of claim 1, The cations of the ionic liquid are ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, ceriazolium, An antistatic composition according to claim 1, wherein the antistatic composition is selected from the group consisting of triazium and guanidinium. The method of claim 1, The anion of the ionic liquid is an internal antistatic composition, characterized in that selected from the group consisting of halogen, sulfate, sulfonate, amide, imide, borate, phosphate, antimonate, decanate and cobalt tetra-carbonyl. . The antistatic product of claim 1, wherein the antistatic composition according to any one of claims 1 to 5 is prepared by mixing 10 to 60 parts by weight with respect to the polymer resin. The method of claim 6, Antistatic product, characterized in that containing 0.1 to 5 parts by weight of a compatibilizer with respect to the polymer resin in the mixing process. The method of claim 6, Antistatic product, characterized in that the antistatic product is an antistatic sheet or film. The method of claim 6, The polymer resin may be acrylonitrile rubber, fluorine rubber, silicone rubber, ethylene propylene rubber, urethane rubber, chloroprene rubber, styrene butadiene rubber, butyl rubber, chlorosulfonate propylene rubber, polymer sulfide rubber, acrylate rubber, epicro At least one synthetic rubber selected from reedrin rubber and acrylonitrile ethylene rubber; Thermoset polyurethanes; Thermoplastic polyurethanes; Polyvinyl chloride; Polyvinyl alcohol; Polyvinyl acetal; ABS; SBS; Polycarbonate; Polypropylene; Polyethylene; polystyrene; nylon; And polyesters alone or mixtures thereof selected from the group consisting of polyesters. The method of claim 6, On at least one side of the antistatic product Per 100 parts by weight of the total composition 5 to 30 parts by weight of the curable binder; 0.1 to 15 parts by weight of carbon nanotubes; 0.1 to 5 parts by weight of at least one additive selected from the group consisting of dispersants, slip agents, flow improvers, antiblocking agents and ultraviolet stabilizers; And An antistatic product comprising an antistatic coating layer comprising 50 to 90 parts by weight of an organic solvent. The method of claim 10, The curable binder is a thermosetting binder which is a single resin or a mixture thereof selected from the group consisting of acrylic resins, urethane resins, urethane-acrylic copolymers, ester resins, ether resins, amide resins, epoxy resins and melamine resins. Antistatic product characterized by. The method of claim 10, The curable binder is an antistatic product, characterized in that the photocurable binder is a single or a mixture thereof selected from the group consisting of acrylic, urethane-based and urethane-acrylic mono or oligomers. An antistatic tray, characterized in that manufactured by vacuum forming the antistatic product of claim 6. An antistatic tray, wherein the antistatic product of claim 10 is manufactured by vacuum forming.