KR20200014678A - Antistatic photho-curable resin composition, antistactic plastic sheet prepared by using this and manufacturing method for the sames - Google Patents

Abstract

The present invention relates to: a high-performance antistatic photo-curable resin composition; a method for manufacturing a plastic or plastic plate using the same; and an antistatic plastic manufactured from the same. More specifically, the present invention relates to: a photo-curable resin composition containing a novel carbon nanotube having particularly excellent dispersibility of a carbon nanotube-containing photocurable resin composition, which is still lacking in an existing carbon nanotube-containing photocurable composition, thereby being able to further accelerate photocuring reaction and maintain stability in a long term; a method for manufacturing a plastic or plastic plate using the same; and an antistatic plastic manufactured from the same.

Description

High performance antistatic photocurable resin composition, uninterruptible panel using the same, and method for manufacturing thereof {ANTISTATIC PHOTHO-CURABLE RESIN COMPOSITION, ANTISTACTIC PLASTIC SHEET PREPARED BY USING THIS AND MANUFACTURING METHOD FOR THE SAMES}

The present invention relates to a high performance antistatic photocurable resin composition, a method for producing a plastic or plastic sheet using the same, and an uninterrupted plastic produced through the same.

More specifically, the present invention is particularly excellent in the dispersibility of the carbon nanotube-containing photocurable resin composition still lacking in the conventional carbon nanotube-containing photocurable composition, further promotes the photocuring reaction, long-term dispersibility and stability The present invention relates to a new carbon nanotube-containing photocurable resin composition which can be maintained, and a method for producing a plastic or plastic sheet using the same, and an uninterrupted plastic produced through the same.

Recently, damages are generated due to the generation of static electricity in various fields ranging from various electronic devices and industrial sites.

More specifically, conventionally charged plastics are used as partitions for dividing the floor or wall area of the clean room of the semiconductor industry, and are used for various purposes such as protective covers of semiconductor equipment, medical equipment and electronic products of the medical industry. It is used a lot.

However, in the case of plastics, due to the large surface electric resistance, it causes a phenomenon of electrification (electrostatic) on the surface, which causes dust adsorption problems, and sparks caused by electrification (electrostatic). It is very likely to be a big problem in the semiconductor industry that requires ultra-high purity products.

In order to solve this problem, an antistatic coating layer is formed on the surface of the plastic, and the material of the antistatic coating layer includes a conductive coating liquid composed of a conductive organic material, a conductive coating liquid composed of an inorganic oxide, a conductive coating liquid containing carbon, and the like. Antistatic coating layer coating method is widely used in industrial sites. However, the antistatic coating liquid containing the low molecular weight or polymer conductive material is regarded as a disadvantage that the expiration date of the charging function is very short, and the long-term antistatic performance is poor due to decomposition by ultraviolet rays. In addition, metal-based materials such as ITO, ATO, or silver nanowires are difficult to popularize due to complex manufacturing processes, low yields, and high prices, and are practically limited in use for semiconductor walls or clean rooms. In addition, a large amount is required to have sufficient antistatic performance, and when the amount is increased, the color is reduced, which significantly reduces the transparency, which is disadvantageous for applications having high light transmittance.

In addition, in the case of multiwall carbon nanotubes and inorganic oxides, a large amount must be added to achieve the desired antistatic performance, and in the case of carbon nanotubes, van der walls force Because of the tendency to agglomerate, it is difficult to stably mix in the antistatic coating solution containing the polymer material, which makes it difficult to store for a long time and has a disadvantage of affecting the color and transmittance of the final product.

 In order to solve the above problems, by using a chemical surface treatment method using a strong acid such as sulfuric acid to increase the compatibility with the organic material by introducing oxygen functional groups such as carboxyl group (hydroxyl group) and hydroxyl group (hydroxyl group) on the surface of the carbon nanotubes. The method has been widely applied, but the surface of the carbon nanotubes are damaged, so there is a disadvantage in that the inherent electrical and mechanical properties cannot be exhibited.

Accordingly, the general method of dispersing carbon nanotubes in an organic solvent without damaging the surface has been applied. However, as mentioned above, the carbon nanotubes are agglomerated with a strong bonding force due to van der Waals force of the carbon nanotubes, thereby securing dispersion stability and storage stability. There was a difficulty.

Therefore, in order to apply the carbon nanotubes to the conductive coating liquid for forming the antistatic coating layer, the surface of the carbon nanotubes having improved dispersibility and miscibility with excellent bonding strength between the organic solvent and the polymer resin without damaging the carbon nanotubes. There is a need for a treatment method, and stability and dispersibility are secured in the long term, and a need for solving the problem of lowering light transmittance has emerged.

An object of the present invention has excellent antistatic properties of 10 ⁹ Ω / sq or less, in particular, the antistatic properties are maintained for a long time can exhibit almost permanent antistatic properties, high transmittance, excellent transparency, scratch resistance The present invention provides a high-performance antistatic photocurable resin composition having excellent antistatic properties with low surface scratches and excellent adhesion to various substrates. In addition, to provide an uninterruptible panel having excellent antistatic properties prepared by coating the high performance antistatic photocurable resin composition.

In addition, the present invention solves the problems such as re-agglomeration or light transmittance decrease even when the photocurable resin composition is stored for a long time to maintain the dispersibility and stability even during long-term storage coating using the photocurable resin composition It is to provide a new single-walled carbon nanotube-containing antistatic photocurable resin composition that can have a significantly improved light transmittance.

More specifically, a high performance antistatic spectacle including a single wall carbon nanotube (SWCNT) as an antistatic agent, and more specifically a single wall carbon nanotube surface-coated with a polymer having a carboxylic acid group. It is an object to provide a chemical conversion resin composition. In addition, it is an object to provide an uninterrupted plastic by coating on a plastic or plastic sheet using this.

In the present invention, especially when the compound having a sulfonic acid group and (poly) alkylene glycol is included, dispersibility and long-term storage stability is significantly increased, dispersibility and stability decrease with time is minimized to coat and cure the substrate and substrate The present invention provides a new type of single-walled carbon nanotube-containing photocurable resin composition which exhibits excellent physical properties whose surface resistance is not related to the storage period of the composition.

In particular, since it includes a single-walled carbon nanotube surface-modified with a polymer having a carboxylic acid group, excellent dispersibility, there is almost no agglomeration phenomenon of the photocurable resin composition with time, so the UV transmittance at 370nm is significantly low, changes over time The ultraviolet ray transmittance according to the present invention is hardly changed, and a new photocurable resin composition in which ultraviolet curing is remarkably well provided is provided.

The present invention also relates to a method for producing a high performance antistatic photocurable resin composition used in a transparent plastic sheet, a coating method using the same, and a permanent antistatic plastic produced by using the same.

More specifically, to overcome the chemical resistance, scratch resistance and abrasion resistance, which is one of the disadvantages of plastics, and to provide an antistatic plastic sheet having a permanent function for a further use period.

In addition, the photocurable resin composition of the present invention to provide a photocurable resin composition and a panel prepared therefrom which significantly improved the uniformity of the surface resistance when photocuring.

The high performance antistatic photocurable resin composition according to the present invention comprises an acrylate composition comprising a photocurable polyfunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate oligomer; Photoinitiators; Single-walled carbon nanotubes surface-modified with a polymer having a carboxylic acid group;

At least one function improving agent selected from compounds having sulfonic acid groups and alkylene glycols; And a solvent; and the like, wherein the high performance antistatic photocurable resin composition has a transmittance of 90% or more and a surface hardness of 1H or more when forming a hard coat film.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, the compound having a sulfonic acid group is camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, xylenesulfonic acid, cumene It may include any one or two or more compounds selected from sulfonic acid and poly (styrenesulfonic acid) and the like or salts thereof.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, the acrylate composition may further include a monofunctional (meth) acrylate monomer.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, the photocurable polyfunctional (meth) acrylate-based oligomer may include a urethane (meth) acrylate-based oligomer.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, the antistatic photocurable resin composition has a photoinitiator 0.01 to 10 parts by weight, carboxylic acid group with respect to 100 parts by weight of the acrylate composition It may include 0.001 to 2 parts by weight of the surface-modified single-walled carbon nanotubes, 0.1 to 10 parts by weight of the compound having a sulfonic acid group, 0.01 to 10 parts by weight of alkylene glycol and 0.1 to 100 parts by weight of the solvent.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, the antistatic photocurable resin composition may further include a smoothing agent.

In the high performance antistatic photocurable resin composition according to an embodiment of the present invention, it may further include any one or a mixture of two or more selected from conductive polymers or conductive metal particles.

In the uninterruptible panel on which the high performance antistatic hard coating film according to an embodiment of the present invention is formed, the high performance antistatic photocurable resin composition may include a cured coating on the surface of the substrate.

In the uninterruptible panel on which the high performance antistatic hard coating film is formed according to an embodiment of the present invention, the high performance antistatic hard coating film may include a surface resistance of 10 ⁹ Ω / sq or less.

In the uninterruptible panel on which the high performance antistatic hard coating film is formed according to an embodiment of the present invention, the high performance antistatic hard coating film may include a transmittance of 90% or more and a surface hardness of 1H or more.

In the method for manufacturing an uninterruptible panel according to an embodiment of the present invention, the method may include coating a high-performance antistatic photocurable resin composition on a substrate, drying, and ultraviolet curing.

The present invention utilizes a high-performance photocurable resin composition as an antistatic coating liquid composition having a permanent function to implement a thin film through a flow coating and spray coating process on a plastic or plastic sheet, which is a conventional antistatic Compared with the coating liquid composition has a long and stable antistatic function can be implemented.

In addition, the color and transmittance are remarkably excellent and stable compared with the antistatic coating liquid used as a conductive material such as inorganic oxide, carbon black, ITO, ATO, and the like.

In addition, the present invention has the advantage that can be given an additional function of scratch resistance, chemical resistance, wear resistance.

In addition, the present invention does not re-aggregate in the long-term even after manufacturing the photocurable resin composition, the UV transmittance is still maintained, that is, the UV transmittance hardly changes over time, the coating layer formed during the hard coating using the photocurable resin composition In this case, the transmittance is remarkably excellent in the visible region, but the surface resistance is low.

In addition, the photocuring agent composition has the advantage of showing a significant long-term storage stability with little change in surface resistance when the photocuring after coating or even when exported to the ship for a long time storage.

In addition, there is an advantage that it has excellent stability that the change of surface resistance is minimized even under the influence of moisture.

In addition, the uninterruptible plastic of the present invention may have high transmittance and stable surface resistance (permanent antistatic function) of 1 to 10 years, and excellent in transmittance as compared to the organic conductive antistatic coating solution using a conventional conductive polymer. It also has the effect of having long-term surface resistance stability. In addition, it has the advantage of achieving a high transmittance compared to the permanent antistatic coating liquid and the plate produced through the conductive conductivity through the metal oxide containing ATO or ITO.

1 is a TEM photograph of surface-modified SWCNT powder.
2 is a TEM photograph of SWCNT surface modified with polyacrylic acid.

DETAILED DESCRIPTION Hereinafter, the present invention will be described in more detail with reference to the accompanying examples or embodiments. However, the following specific examples or examples are only one reference for describing the present invention in detail, but the present invention is not limited thereto and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description in the present invention are only for effectively describing specific embodiments and are not intended to limit the present invention.

Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

In the present invention, "(meth) acrylate" is used as a generic term for acrylate and methacrylate.

The term 'high performance antistatic' in the present invention means the same as antistatic or uninterruptible, and means that the antistatic performance is very excellent with a surface resistance of 10 ⁹ Ω / sq or less.

In order to achieve the above object, the inventors of the present invention add a surface-modified single-walled carbon nanotube (SWCNT) and a functional enhancer to a polymer having a carboxylic acid group to further improve dispersibility and stability, and maintain excellent conductivity. It has been found that the antistatic photocurable resin composition can have a permanent antistatic function.

In addition, in the case of adding a single-walled carbon nanotube (SWCNT) surface-modified with a polymer having a carboxylic acid group, even when a small amount is used, it is specifically 0.001 to 2 parts by weight based on 100 parts by weight of the acrylate composition It was found that even when included as a content, it is possible to provide a permanent high performance antistatic hard coating film having a surface resistance of 10 ^{9 9} / sq or less, a very small change in surface resistance, and a transmittance of 90% or more.

In addition, an acrylate composition comprising a photocurable polyfunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate oligomer, a photoinitiator, a single wall carbon nanotube surface-modified with a polymer having a carboxylic acid group, and a sulfonic acid group By providing a high-performance antistatic photocurable resin composition comprising at least one functional improving agent and a solvent selected from the compound and alkylene glycol having a branch, excellent scratch resistance and adhesion, remarkably high transmittance, improved chemical resistance The present invention has been completed by discovering that it can overcome the disadvantages of plastic or plastic sheeting.

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

In one aspect of the present invention, a high performance antistatic photocurable resin composition comprises an acrylate composition, a photoinitiator, a carboxylic acid group comprising a photocurable polyfunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate oligomer. It includes a single-walled carbon nanotube surface-modified with a polymer having a compound, a compound having a sulfonic acid group and at least one functional enhancer and a solvent selected from alkylene glycol.

The acrylate composition constituting the high performance antistatic photocurable resin composition may further include a monofunctional (meth) acrylate monomer.

The term 'monofunctional' means that it includes one functional group selected from an acrylate group, a methacrylate group, and a vinyl group having photoreactivity,

The term 'multifunctional' means that it includes two or more functional groups selected from an acrylate group, a methacrylate group, and a vinyl group having photoreactivity.

Specifically, the monofunctional (meth) acrylate monomer may be included in 0 to 90wt% based on the total weight of the acrylate composition.

In addition, the multifunctional (meth) acrylate monomer may be included in 30 to 90wt% based on the total weight of the acrylate composition.

In addition, the multifunctional (meth) acrylate oligomer may be included in 10 to 60wt% with respect to the total weight of the acrylate composition.

As a more specific example, the high-performance antistatic photocurable resin composition may be 0.01 to 10 parts by weight of a photoinitiator, surface-modified single-walled carbon nanotubes 0.001 to 100 parts by weight of the acrylate-based composition. It may include 2 parts by weight, 0.1 to 10 parts by weight of the compound having a sulfonic acid group, 0.01 to 10 parts by weight of alkylene glycol and 0.1 to 100 parts by weight of the solvent.

In one embodiment of the present invention, the acrylate composition may include a photocurable urethane (meth) acrylate oligomer and the like as the multifunctional (meth) acrylate oligomer.

More specifically, the photocurable multifunctional (meth) acrylate-based oligomer may further include a polyester acrylate oligomer, an epoxy acrylate oligomer, an acrylic acrylate oligomer, or any mixture thereof, as needed. Specifically, the amount may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylate composition, but is not particularly limited thereto.

Next, the said photocurable polyfunctional (meth) acrylate type monomer of this invention is demonstrated concretely.

The photocurable polyfunctional (meth) acrylate-based monomer may comprise a reactive monomer, the reactive monomer is a monomer polymerizable by a photoinitiator, two selected from the acrylate group, methacrylate group and vinyl group in the molecular structure It may include a mixture of monomers having the above functional groups.

Specifically, the photocurable polyfunctional (meth) acrylate-based monomer may be used by mixing one or more monomers having 2 to 6 functional groups or more various functional groups, the working viscosity of the resin composition, substrate adhesion, scratch resistance In consideration of the properties, it is possible to adjust the viscosity and scratch resistance and the like by using the 2 to 6 functional monomers.

The photocurable multifunctional (meth) acrylate monomer may be included in an amount of 30 to 90 wt% based on the total weight of the acrylate composition.

In a more specific aspect, the multi-functional (meth) acrylate-based monomer may include a 2 to 6 functional (meth) acrylate-based monomer, 2 to 6 functional (relative to the total weight of the acrylate composition ( Meta) acrylate monomer may be included in 30 to 90 wt% with respect to the total weight of the acrylate composition, specifically 40 to 80 wt%, more specifically as included in 50 to 70 wt% The coating viscosity and scratch resistance of the photocurable resin composition may be adjusted, but is not limited thereto.

The photocurable polyfunctional (meth) acrylate-based monomer may be used as a reactive diluent with good compatibility with the multifunctional (meth) acrylate-based oligomer, and may serve to impart workability of the photocurable resin composition. It may be polymerized by ultraviolet irradiation to serve as a crosslinking agent between polymers.

The polyfunctional (meth) acrylate monomer is not particularly limited, but specific examples thereof include 1,4-butanedioldi (meth) acrylate, 3-methyl-1,5-pentanedioldi (meth) acrylate, 1, 6-hexanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate, 2-methyl-1,8-octanedioldi (meth) acrylate, 2-butyl-2-ethyl-1,3- Propanedioldi (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, ethylene glycoldi (meth) acrylate, diethylene glycoldi (meth) acrylate, triethylene glycoldi (meth) acrylate, Di (meth) acrylate of dihydric alcohols such as dipropylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Tris (2-hydroxyethyl) isocyanu 2 moles of ethylene oxide or propylene oxide to 1 mole of di (meth) acrylate and diol of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol Di (meth) acrylate, trimethylol propane tri (meth) acrylate of the diol obtained by addition, ethylene oxide modified trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, ditrimethyl All propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) There may be mentioned acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These polyfunctional (meth) acrylates may be used by 1 type, or may be used together in 2 or more types.

In addition, the polyfunctional (meth) acrylate monomer having six functional groups is not particularly limited, but specific examples thereof include Aronix M403 (pentaerythritol hexaacrylate, DPHA, Doagose Co.), 6-functional (meth) acryl Hexafunctional (meth) acrylates, such as the hexafunctional acrylate (DPCA-60, Kayarad) which have six phosphazene monomers and six pentyleneoxy chains, can be used.

In addition, the polyfunctional (meth) acrylate monomer having five functional groups is not particularly limited, but specific examples thereof include 5-functional (meth) acrylates such as dipentaerythritol penta (meth) acrylate. It is not limited.

The polyfunctional (meth) acrylate monomer having four functional groups is not particularly limited, but specific examples thereof include tetrafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, but are not limited thereto. It is not.

The polyfunctional (meth) acrylate monomer having three or more functional groups is not particularly limited, but specific examples thereof include pentaerythritol such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate (DPHA). Or dipentaerythritol-based polyfunctional acrylate, trimetholpropane triacrylate (TMPTA), ethylene oxide addition type trimetholpropane triacrylate (EO-TMPTA), glycerin propylene oxide addition type triacrylate (PETTA), or the like. Can be.

In addition, the polyfunctional (meth) acrylate monomer having two functional groups is not particularly limited, but specific examples thereof include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, neophenylglycol diacrylate, Neopentylglycol diacrylate, nonylpropylene glycol diacrylate, dipropylene glycol diacrylate, diethylene glycol di (meth) acrylate, ethylene glycol dimethacrylate, tetratriethylene glycol diacrylate, ethoxylate di Bisphenol a di (meth) acrylate, triethylene glycol diacrylate, etc. can be used.

The monofunctional (meth) acrylate monomer having one functional group is not particularly limited, but specific examples thereof include acrylic monomers such as alkyl methacrylate and alkyl acrylate, and more specifically, for example, methyl methacrylate. , Ethyl acrylate, methyl acrylate, propyl acrylate, hexyl acrylate, butyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-phenoxyethyl acrylate, ethylene oxide addition type phenoxyethyl acrylate, 2 Various copolymerization monomers, such as-(2-ethoxy) ethyl acrylate, nonylphenyl acrylate, epoxy monoacrylate, oxyethylphenol acrylate and isobornyl (meth) acrylate, can be adopted, but not limited thereto.

In addition, in the present invention, a photocurable (meth) acrylate monomer having a hydroxyl group may be included, if necessary. Specifically, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). ) Acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylic Mono (meth) acrylates of dihydric alcohols such as late, neopentyl glycol mono (meth) acrylate, and hydroxy pivalate neopentyl glycol mono (meth) acrylate; Trimethylolpropanedi (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropanedi (meth) acrylate, glycerin di (meth) acrylate, bis Hydroxyl group which modified | denatured mono- or di (meth) acrylate of trihydric alcohols, such as (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or these alcoholic hydroxyl groups by (epsilon) -caprolactone Mono and di (meth) acrylates having; Compound which has monofunctional hydroxyl group and trifunctional or more (meth) acryloyl group, such as pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate, or Polyfunctional (meth) acrylate which has a hydroxyl group which modified | denatured this compound further into (epsilon) -caprolactone; (Meth) acrylates having oxyalkylene chains such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate ; (Meth) acrylates having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; (Meth) acrylate which has the oxyalkylene chain of random structures, such as a poly (ethylene glycol- tetramethylene glycol) mono (meth) acrylate and a poly (propylene glycol- tetramethylene glycol) mono (meth) acrylate, etc. are mentioned. Although these can be used 1 type or in combination or 2 or more types, it is not specifically limited to these.

Next, the said photocurable polyfunctional (meth) acrylate type oligomer of this invention is demonstrated concretely.

The photocurable polyfunctional (meth) acrylate-based oligomer may include a polyfunctional urethane (meth) acrylate-based oligomer and the like, and 10 to 60wt%, more specifically 20 to 20% based on the total weight of the acrylate-based composition. 50 wt%, more specifically, 20 to 40 wt%, preferably 25 to 40 wt%, so that sufficient hardness, abrasion resistance and scratch resistance of the hard coating layer or film desired in the present invention can be ensured.

Specifically, the multifunctional (meth) acrylate-based oligomer may be used by mixing at least one oligomer having 2 to 10 functional groups or various functional groups, and the working viscosity and substrate adhesion, wear resistance and scratch resistance of the resin composition In consideration of the properties, it is possible to adjust the viscosity, abrasion resistance and scratch resistance using a multifunctional (meth) acrylate-based oligomer having 6 to 10 functional groups.

Specifically, when the polyfunctional urethane (meth) acrylate-based oligomer having the functional group number range is included, the surface smoothness of the hard coating layer or the film is better, and light transmittance may also be improved.

More specifically, when the number of functional groups of the multifunctional urethane (meth) acrylate-based oligomer is greater than 10, the wear resistance of the surface protective layer may be inferior when the obtained coating layer is formed, and weather resistance and smoothness may be reduced. On the other hand, when the number of functional groups is less than 6, the crosslinking density may decrease, and the abrasion resistance may be insufficient, and the number of the functional groups is not particularly limited, but preferably 6 to 10 functional groups. Specifically, when the number of functional groups is 6 to 10 functional groups, the curing rate is improved while having abrasion resistance and scratch resistance, and may have a good soft coat and moderate softness.

The photocurable polyfunctional (meth) acrylate-based oligomer may include the polyfunctional urethane (meth) acrylate-based oligomer and the like, and, if necessary, polyester acrylate oligomer, epoxy acrylate oligomer, acrylic acrylate oligomer Or any mixture thereof, and the like, and may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylate-based composition, but is not particularly limited thereto.

The photocurable polyfunctional urethane (meth) acrylate-based oligomer may include an aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, and the like, which is included in the high-performance antistatic photocurable resin composition, processability, solvent resistance And physical properties such as hardness and adhesion can be improved.

Specifically, the aliphatic urethane acrylate oligomer is CN8000NS (6-functional group, viscosity 14,000cps @ 25 ℃, Satomer company), CN8007NS (4-functional group, viscosity 1,250cps @ 25 ℃, Satomer company), CN8009NS (trifunctional group, viscosity 517cps @ 25 ℃, Satomer), CN8011NS (6-functional group, viscosity 6,800cps @ 25 ℃, Satomer company), CN8881NS (bi-functional group, viscosity 20,000-40,000cps @ 60 ℃, Satomer company), CN9001NS (bi-functional group, viscosity 46,500cps @ 60 ° C, Satomer), CN9010NS (6 functional group, viscosity 2,200cps @ 60 ° C, Satomer company), CN9013NS (9 functional group, viscosity 10,000cps @ 60 ° C, Satomer company), Miramer PU210 (bifunctional group, viscosity 40,000cps @ 25 ℃, Miwon Corporation), Miramer PU340 (trifunctional group, viscosity 75,000cps @ 25 ℃, Miwon Corporation), Miramer PU610 (6-functional group, viscosity 100,000cps @ 25 ℃, Miwon Corporation), Miramer PU620 (6-functional group, viscosity 60,000cps @ 25 ℃, Miwon Corporation), Miramer PU664 (6 functional group, viscosity 61,000 @ 25 ℃, Miwon Corporation), Miramer SC2153 (10 functional group, viscosity 140,000cps @ 25 ℃, Miwon Corporation), Everec 1290 (6 Functional group, molecular weight (MW) about 1,000, SK Cytec), ebecryl 1290K (hexafunctional group, molecular weight (MW) about 1,000, SK Cytec) and ebecryl 5129 (hexafunctional group, molecular weight about 800, SKC Saitec), or any mixture thereof, and the like can be used.

Specifically, the aromatic urethane acrylate oligomer is CN975NS (six functional group, viscosity 500cps @ 60 ° C, Satomer), CN978NS (bifunctional group, viscosity 3,200cps @ 60 ° C, Satomer), Miramer PU280 (bifunctional group, viscosity 50,000 cps @ 25 ℃, Miwon Corporation), Miramer PU640 (6 functional group, viscosity 30,000cps @ 25 ℃, Miwon Corporation), AH-600 (bifunctional group, viscosity 2,000 ~ 4,000cps @ 50 ℃, Kyoeisha) and AT-600 (4-functional group, viscosity 10,000-20,000cps @ 25 degreeC, Kyoeisha company), or arbitrary mixtures thereof, etc. can be used.

The polyfunctional urethane (meth) acrylate-based oligomer may include a 10-functional urethane (meth) acrylate-based oligomer having a 10 functional group, and specific examples thereof include SUO1700B (10-functional urethane acrylate oligomer, Cynthia & C), SC2153 (10 functional urethane acrylate oligomer, Miwon special chemical), Miramer MU9500 (10 functional urethane acrylate oligomer, Miwon specialty chemical), UV-1700 (10 functional urethane acrylate, Nippon Kosei Co., Ltd.), MU9800 ( 10-functional urethane (meth) acrylate-based oligomers such as urethane acrylate oligomer, Miwon Corporation) and UV1000 (10-functional urethane acrylate oligomer, Shin Art & C), but is not necessarily limited thereto.

Specifically, the polyester acrylate oligomer is CN294E (4-functional group, viscosity 5,500cps @ 60 ° C, Satomer), CN7001NS (bifunctional group, viscosity 2,500cps @ 25 ° C, Satomer), Miramer PS460 (bi-functional group, viscosity 40,000cps @ 25 ℃, Miwon Corporation), Miramer PS610 (6 functional group, viscosity 40,000cps @ 25 ℃, Miwon Corporation), ebecryl 830 (6 functional groups, viscosity 50,000cps @ 25 ℃, SK Cytec), ebecryl 800 ( Tetrafunctional groups, viscosity 14,000 cps @ 25 ° C., SK Cytec), or any mixture thereof.

Specifically, the above epoxy acrylate oligomer is CN104NS (bifunctional group, viscosity 18,900cps @ 49 ° C, Satomer), CN2003NS (bifunctional group, viscosity 3,495cps @ 60 ° C, Satomer), Miramer PE110 (monofunctional group, viscosity 140cps @ 25 ℃, Miwon Co., Ltd., Miramer PE230 (bifunctional group, viscosity 500cps @ 25 ℃, Miwon Co., Ltd.), Miramer PE320 (trifunctional group, viscosity 12,000cps @ 25 ℃, Miwon Co., Ltd.), ebecryl 600 (bifunctional group) , Viscosities 3,000 cps @ 25 ° C., SK Cytec), ebecryl 3416 (tetrafunctional group, viscosities 18,000 cps @ 25 ° C., SKC Saitec), or any mixture thereof can be used.

Specifically, the above-mentioned acrylic acrylate oligomer is evercryl 740-40TP (viscosity 8,500cps @ 25 ℃, SK Cytec), evercryl 741 (viscosity 4,500cps @ 25 ℃, SK Cytec), evercryl 767 (viscosity 8,500cps @ 25 ° C., SK Cytec), Ebecryl 1710 (viscosity 26,000 cps @ 25 ° C., SK Cytec), or any mixture thereof can be used.

It is preferable to use the polyfunctional urethane (meth) acrylate type | system | group oligomer whose weight average molecular weights (Mw) are 500-12,000. If the weight average molecular weight is less than 500, the crosslinking density may be increased, and workability may be decreased. If the weight average molecular weight is more than 12,000, the viscosity may be increased, so that the coating may be restricted using the photocurable resin composition of the present invention. have.

In one embodiment, the acrylate composition of the present invention comprises a photocurable polyfunctional (meth) acrylate monomer having 2 to 6 functional groups, and a photocurable polyfunctional urethane (meth) having 6 to 10 functional groups It may be used to mix the acrylate oligomer.

In one embodiment of the present invention, the photoinitiator may be used as a photoinitiator as an initiator capable of initiating polymerization by ultraviolet light, and is not particularly limited, such a photoinitiator, diethoxyacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, benzyldimethyl ketal, 1- (4-iso Propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone Acetophenone compounds such as 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone ; Benzoin compounds such as benzoin, benzoin methyl ether and benzoin isopropyl ether; Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, such as benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester System compounds; Benzophenone, o-benzoylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ' Such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, and 4-methylbenzophenone Benzophenone compounds; Thioxanthone compounds such as 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2,4-dichloro thioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2 -(4-methylphenylsulfonyl) propane-1-one, hydroxycyclohexylphenyl ketone, 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinyl-1-propane, hydroxyketone, Benzyldimethylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bisacylphosphineoxide, diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide and phosphine oxide phenyl Bis (2,3,6-trimethylbenzoyl) and the like can be used. These can be used individually or in mixture of 2 or more types. The photoinitiator may be added to 0.01 to 10 parts by weight, specifically 0.01 to 5 parts by weight, more specifically 0.01 to 3 parts by weight based on 100 parts by weight of the acrylate composition, but is not particularly limited thereto.

Next, the solvent used by this invention is demonstrated concretely.

The solvent used in the present invention can be applied by selecting a suitable solvent according to the purpose of use, and can be used to adjust the mixture to have the desired properties.

In the present invention, the solvent comprises a first solvent and a second solvent, the first solvent is a solvent used to prepare a surface-modified single-walled carbon nanotube with a polymer having a carboxylic acid group of the present invention, 2 solvent is a solvent for mixing the acrylate composition of the present invention.

The second solvent is a solvent for mixing the acrylate composition of the present invention, may include a solvent suitable for forming a coating layer, can stably dissolve the acrylate composition, the high performance antistatic The viscosity of a photocurable resin composition can be adjusted and leveling can be provided.

Specifically, the second solvent may be mixed with the acrylate-based composition, an organic solvent may be used for proper fluidity and coating properties of the high performance antistatic photocurable resin composition, for example, methanol, ethanol, Alcohol solvents such as isopropyl alcohol, butanol, alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl Ketone solvents such as propyl ketone and cyclonucleone dione, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, Ethylene glycol is an ether-based solvents, benzene, ether, such as 2-ethyl haeksil be used alone or mixed with an aromatic solvent such as toluene, xylene.

In a preferable embodiment, the second solvent for mixing the acrylate composition can be used as the ether solvent, without limitation, as long as it is an alkylene glycol monoalkyl ether solvent, and is generally obtained from a long chain olefin having many carbon atoms. It has a dissolving power and low pour point and also has a good function as a surfactant.

In the present invention, in particular, the alkylene glycol monoalkyl ether solvent may be included, preferably propylene glycol monomethyl ether may be used, 0.1 to 100 parts by weight based on 100 parts by weight of the acrylate monomer composition Can be used

More specifically, the alkylene glycol monoalkyl ether solvent is 0.1 to 50 parts by weight, more specifically 0.1 to 30 parts by weight, more specifically 0.1 to 10 parts by weight, based on 100 parts by weight of the acrylate monomer composition. Preferably 0.1 to 5 parts by weight, it may be included in the above range can be effectively dissolved the acrylate composition of the present invention, more excellent surface resistance and surface smoothness and long-term surface resistance change rate is minimized A composition can be provided. It is also desirable because it can play an important role in forming a uniform coating layer without defects.

Next, a single-walled carbon nanotube (SWCNT) surface-modified with a polymer having the carboxylic acid group will be described.

In the present invention, by adopting single-walled carbon nanotubes, it is very excellent in that it can have remarkable dispersibility, transparency, and excellent long-term performance retention compared to those used in multi-wall carbon nanotubes, and especially the surface By modifying or surface coating single-walled carbon nanotubes using polymers or copolymers containing carboxylic acid groups such as acrylic acid or methacrylic acid as modifiers, the color change due to the use of single-walled carbon nanotubes is significantly less, The transparency and permeability are very good and can provide better coating properties.

In the present invention, the polymer having a carboxylic acid group on the surface of the single-walled carbon nanotubes can be easily surface-modified or surface-coated without damaging the single-walled carbon nanotubes and without a separate process such as chemical treatment. In addition, since the surface of the single-walled carbon nanotubes is not damaged, it can be used without degrading the inherent mechanical and electrical properties, thereby providing more excellent antistatic property to the antistatic photocurable resin composition desired in the present invention. .

In one aspect, the polymer having a carboxylic acid group may be a polymer having a carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid, or a copolymer prepared by including these monomers. It may be one containing a mole percent or more units.

The copolymerizable methacryl-based or acrylic monomers are acrylic monomers such as alkyl methacrylate and alkyl acrylate, for example, methyl methacrylate, ethyl acrylate, methyl acrylate, propyl acrylate, hexyl acrylate and butyl acryl. Latex, 2-hydroxypropyl (meth) acrylate, 2-phenoxyethyl acrylate, ethylene oxide addition type phenoxyethyl acrylate, 2- (2-ethoxy) ethyl acrylate, nonylphenyl acrylate, epoxy monoacrylic Various copolymerization monomers, such as a rate, an oxyethyl phenol acrylate, isobonyl (meth) acrylate, are employ | adopted, but it is not limited to this, Preferably, the copolymer of polyacrylic acid, polymethyl methacrylate, etc. can be used.

In the present invention, the solvent comprises a first solvent and a second solvent, the first solvent is a solvent used to prepare a surface-modified single-walled carbon nanotube with a polymer having a carboxylic acid group of the present invention.

The first solvent may stably mix and disperse the single-walled carbon nanotubes surface-modified with the polymer having the carboxylic acid group, and may be mixed with the polymer and the single-walled carbon nanotube having the carboxylic acid group to form the single-walled carbon. Surface modification or surface coating of the nanotubes can be performed more effectively.

The first solvent may be included in 0.1 to 100 parts by weight, based on 100 parts by weight of the acrylate monomer composition, 0.1 to 50 parts by weight, more specifically 0.1 to 40 parts by weight may be included.

Examples of suitable first solvents include 1,4-dioxane, acetone, acetonitrile, chloroform, chlorophenol, cyclohexane, cyclohexanone, cyclopentanone, dichloromethane and diethyl. Acetate, diethyl ketone, dimethyl carbonate, dimethylformamide, dimethylsulfoxide, ethanol, ethyl acetate, m-cresol, mono- and di-alkyl substituted glycols, N, N-dimethylacetamide, p-chlorophenol, 1,2-propanediol, 1-pentanol, 1-propanol, 2-hexanone, 2-methoxyethanol, 2-methyl-2-propanol, 2-octanone, 2-propanol, 3 -Pentanone, 4-methyl-2-pentanone, hexafluoroisopropanol, methanol, methyl acetate, methyl acetoacetate, methyl ethyl ketone, methyl propyl ketone, n-methylpyrrolidone-2, n-pentyl acetate, phenol Tetrafluoro-n-propanol, tetrafluoroisopropanol, Trad tetrahydrofuran, toluene, xylene and the like, and water, preferably, but can use the 1-propanol is not particularly limited.

In one aspect of the present invention, the method for surface-modifying a single-walled carbon nanotube with a carboxylic acid group may be carried out by vigorously mixing the polymer having the carboxylic acid group, the first solvent, or the single-walled carbon nanotube, or having the carboxylic acid group. By injecting the single-walled carbon nanotubes during the polymerization of the polymer, the carboxylic acid, which is a polar group, may be adsorbed and coated on the surface of the single-walled carbon nanotubes.

For the mixing, a well-known mixing and homogeneous apparatus may be used, and a disperser, a nano high pressure disperser, an impeller, an ultrasonic disperser, a grinder, a three roll mill, a paste mixer, a centrifuge, and the like may be used. When using the single-walled carbon nanotubes of the present invention can be uniformly mixed and dispersed in the polymer having the first solvent and the carboxylic acid group, the carboxyl is uniformly coated with a polymer having a carboxylic acid group on the surface It is preferable in that it can manufacture a single-walled carbon nanotube surface-modified with a polymer having an acid group.

In the present invention, after dispersing the SWCNT without surface modification in the SEM photograph (FIG. 1) lacks the connection between the SWCNT and SWCNT, but the surface modification of the present invention (FIG. 2) is SWCNT and SWCNT cross each other, well fused As a result, it can be seen that a network structure connected to each other is formed, and thus, there are many improvements in physical properties.

In one embodiment of the present invention, the content of the single-walled carbon nanotubes surface-modified with the polymer resin having the carboxylic acid group may be added in an amount of 0.001 to 1 parts by weight based on 100 parts by weight of the acrylate composition. If the content is added less than 0.001 parts by weight, the effect of lowering the surface resistance is insignificant, and if it exceeds 1 part by weight, the surface resistance can be lowered, but the adhesion may be lowered, the transmittance is lowered, the visibility may be lowered . More specifically, it may be included in 0.001 to 1 parts by weight, more specifically 0.001 to 0.1 parts by weight, and more specifically, may be included in 0.001 to 0.01 parts by weight, and even in the above range, the surface resistance may satisfy 10 ⁹ Ω / sq or less. Can be.

In one aspect of the present invention, the high performance antistatic photocurable resin composition may further include a leveling agent. When the smoothing agent is coated with the composition on the surface of the panel substrate, it imparts a surface smoothness and surface slip function, and at the same time give a scratch resistance effect, specifically, for example, silicone acrylate-based smoothing agent, non-silicone acrylic Rate-based levelers, acrylate polysiloxane-based levelers and the like can be used. Commercially available Ebecryl 350, UCB Chemical's silicone acrylate. The leveling agent may be included in an amount of 0.001 to 3 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate monomer composition.

Next, the function improving agent of this invention is demonstrated.

The function improving agent of the present invention may include at least one selected from a compound having a sulfonic acid group and an alkylene glycol, and may specifically include the alkylene glycol together with the compound having the sulfonic acid group.

Next, the compound which has a sulfonic acid group is demonstrated.

The compound having a sulfonic acid group may serve to induce stable mixing of the single-walled carbon nanotube surface-modified with the polymer having the carboxylic acid group and the acrylate-based composition as the present function improving agent. It is possible to prevent the carboxyl groups on the surface of the single-walled carbon nanotubes surface-modified with a polymer having a carboxylic acid group from colliding with each other to prevent the dispersibility of the single-walled carbon nanotubes from colliding with each other.

In particular, when the compound having a sulfonic acid group is used, the high-performance antistatic photocurable resin composition of the present invention hardly occurs aggregation and precipitation with time, and thus excellent long-term dispersibility and long-term stability, and UV transmittance according to the change over time Is hardly changed, UV curing may occur remarkably well, and the photocurable resin composition comprising the compound having the sulfonic acid group as a function enhancer, the coating layer or thin film having a significantly improved transmittance while having a low surface resistance during hard coating on a substrate or a substrate Can be formed.

Specific examples of the compound having a sulfonic acid group include, for example, camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and poly (styrenesulfonic acid) or salts thereof. It may include any one or two or more selected compounds, but if the compound having a sulfonic acid group that can serve as a desired function enhancer is not particularly limited thereto, when using the p-toluenesulfonic acid When the hard coating layer is formed, the surface resistance can be lowered and the transmittance can be improved, which can be maintained for a long time.

In one embodiment of the present invention, the content of the compound having a sulfonic acid group may be included in an amount of 0.1 to 5 parts by weight, specifically 0.1 to 3 parts by weight, more specifically 0.1 to 100 parts by weight of the acrylate composition. It may be included in an amount of 1 to 1 part by weight, and the high performance antistatic photocurable resin composition of the present invention may be uniformly and stably mixed according to the above range to maintain long-term dispersibility and stability.

The alkylene glycol is a function enhancer, by simply mixing in the photocurable resin composition of the present invention can improve and improve the conductivity, lower the surface resistance when forming the hard coating layer of the present invention, improve the transmittance, this It is preferable because it can maintain for a long time.

Specifically, the alkylene glycol may be included in an amount of 0.01 to 10 parts by weight, specifically 0.01 to 5 parts by weight, more specifically 0.01 to 3 parts by weight based on 100 parts by weight of the acrylate composition. It may be, as included in the above range can improve and improve the conductivity in the photocurable resin composition of the present invention.

Specifically, the (poly) alkylene glycol is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1, 2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, paraxylene glycol, 1,4-cyclohexane-methanediol, and the like, which may be used alone or in a mixture of two or more. It may be used as, but is not particularly limited to use ethylene glycol.

In one aspect of the present invention, the high performance antistatic photocurable resin composition may further include any one or more components selected from conductive polymers or conductive metal particles to improve conductivity. The mixed state of the single-walled carbon nanotubes surface-modified with the polymer having the carboxylic acid group and the conductive polymer and the conductive metal particles may give an effect of further excellent coating property with the substrate.

The conductive polymer is not particularly limited, but for example, soluble in water-soluble polyaniline, water-soluble polypyrrole, water-soluble polythiophene, water-soluble poly (3,4-ethylenethiophene), derivatives or copolymers thereof, water-soluble and organic solvents It may include one or two or more selected from the group consisting of conjugated electrically conductive polymers.

The conductive metal particles may be used as the material without particular limitation as long as the conductive metal particles are conductive, and for example, metals or metal oxides may be used alone or in combination of two or more thereof. Examples of the metal include, but are not limited to, gold, silver, copper, aluminum, and the like. As an example of a metal oxide, indium-tin oxide (ITO) may be used.

In one aspect of the present invention, the high-performance antistatic photocurable resin composition is a polymerization inhibitor, surface conditioner, antistatic agent, antifoaming agent, viscosity adjuster, light stabilizer, weathering stabilizer, heat stabilizer, ultraviolet absorber, oxidation Additives such as inhibitors, leveling agents, organic pigments, inorganic pigments, pigment dispersants, organic beads; And inorganic fillers such as silicon oxide (silica particles), aluminum oxide, titanium oxide, zirconia, antimony pentoxide, and the like. These can be used individually by 1 type, and can mix and use 2 or more types.

The present invention provides a method for producing an uninterruptible panel comprising the step of coating an antistatic photocurable resin composition on a substrate, drying and ultraviolet curing.

In one aspect, the high performance antistatic photocurable resin composition may be prepared by coating on a transparent plate by various coating methods such as flow coating, spray coating, dip coating and knife coating, and photocuring.

Next, the panel base material of this invention is demonstrated.

The uninterruptible panel according to an aspect of the present invention may be obtained by coating the high performance antistatic photocurable resin composition on at least one surface of a substrate, and irradiating active energy rays to form a cured coating film. Examples of the coating method include die coat, micro gravure coat, gravure coat, roll coat, comma coat, air knife coat, kiss coat, spray coat, orbit coat, dip coat, spinner coat, wheeler coat, brush coating, A solid coat, a wire bar coat, a flow coat, a knife coat by a silk screen, etc. are mentioned.

In addition, when ultraviolet rays are used as active energy rays to cure the composition, as an apparatus for irradiating ultraviolet rays, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, and an electrodeless lamp (fusion lamp) ), A chemical lamp, a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium gadolinium laser, an argon laser, sunlight, an LED, and the like.

The base material of the uninterruptible panel of the present invention may be used without limitation as long as it is a polymer resin used for the panel. Specifically, for example, when high transparency is required, polycarbonate, polyvinyl chloride, polyethylene terephthalate (PET) , Polypropylene, a polymethyl methacrylate-based acrylic resin, polysulfone, polyether ketone, or any one sheet selected from the like can be used.

Usually, since the objective of this invention uses a transparent base material, if the said resin component is a good thing and a normal polymer resin is not specifically limited in terms of providing the antistatic performance of this invention.

In one aspect, the panel according to the present invention is prepared using the high-performance antistatic photocurable resin composition presented above, it may be one having a surface resistance of 10 ⁹ Ω / sq or less.

The uninterruptible panel according to the present invention is prepared using the high performance antistatic photocurable resin composition shown above, and has a surface resistance of 10 ⁹ kPa or less, more specifically 10 ⁶ to 10 ⁹ kPa / Sq, and in the case of polycarbonate sheet The light transmittance is 90% or more, more preferably 95% or more, and the pencil hardness is 1H or more, more preferably 2H or more.

In addition, the surface resistance change rate △ represented by the following formula 1 may be 10 ² Ω / sq or less, more specifically 10 ⁰ to 10 ² Ω, to form a high-performance antistatic hard coating film that can exhibit a permanent antistatic properties can do.

[Equation 1]

ΔS = S2-S1

In Formula 1, S2 is the surface resistance measured after UV irradiation for 20 hours at 480 mJ / ㎠, S1 is the surface resistance measured before UV irradiation.

In addition, the transmittance is more than 90%, more preferably 95% or more remarkably excellent transparency, it is possible to form a high-performance antistatic hard coating film having a surface hardness of 1H or more.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, the present invention is not limited by the following Examples and Comparative Examples.

1. Photocurable resin composition transmittance

In order to confirm the dispersion stability of the photocurable resin composition, the transmittance in the ultraviolet wavelength region of 370 nm was measured by using an ultraviolet-visible spectrophotometer after standing at room temperature for 24 hours.

2. Surface resistance

Surface resistance was measured using an MITSUBISHI HIRESTA MCP-HT450.

Measurement condition Applied voltage: 10V (Change to 100V when exceeding 9.99X10 ¹⁰ during measurement), PROBE: URS TYPE

3. Coping substrate transmittance

The transmittance was measured by using the CM-5 (spectrophotometric) device of Konica Minolta by ASTM D1003-13 (Measurement A).

4. Pencil hardness (Missubishi pencil)

It measured by the method of JISK5600-5-4: 1999.

 Example 1

1) Preparation of single-walled carbon nanotubes surface-modified with polymers having carboxylic acid groups

0.014 g of single-walled carbon nanotubes (diameter: 1.6 ± 0.6 nm, length: 5 μm or more, oxyal), 0.042 g of polyacrylic acid polymer having a weight average molecular weight of 12000, and 99.944 g of 1-propanol (Sigma Aldrich) are placed in a glass beaker. After the mixing process was carried out for 1 hour using a magnetic stirrer to prepare a mixture. Subsequently, SWCNT-Sol was obtained by high pressure spraying at a pressure of 30,000 psi using a high pressure disperser, and centrifuged at 10,000 rpm for 1 hour using a centrifuge to remove undispersed SWCNT and impurities, and then to obtain high purity SWCNT-Sol. Got it. At this time, the weight of the undispersed SWCNT was 0.007g, and the SWCNT surface-modified with polyacrylic acid was 50% yield, finally obtaining 89.730g of high purity SWCNT-Sol dispersed in 1-propanol.

2) Preparation of high performance antistatic photocurable resin composition

In the photocurable acrylate composition, 1.4 g of 10-functional urethane acrylate (SC2153, Miwon Special Chemical), 0.5 g of 6-functional acrylate DPHA (Dipentaerythritolhexaacrylate), dipentaerythritol penta (meth) acrylate 1.4 which is a 5-functional acrylate g, trifunctional acrylate 0.4g of PETA (Pentaerythritoltriacrylate), and 0.4g of butanedioldi (meth) acrylate were prepared from bifunctional acrylate.

In a beaker prepared separately, 0.56 parts by weight of (2-hydroxy-2-methyl-1-phenylpropan-1-one) and propylene glycol methyl ether (PGME) based on 100 parts by weight of the prepared acrylate composition. 10.07 g of a photocurable resin mixture was prepared by mixing 1.4 parts by weight.

10.07 g of the photocurable resin mixture and 89.730 g of the high-purity SWCNT-Sol prepared above were put in a separate beaker, stirred for 10 minutes using a magnetic stirrer, and 0.24 parts by weight of p based on 100 parts by weight of the prepared acrylate composition. Toluene sulfonic acid (para toluenesulfonic acid) was added to prepare a high performance antistatic photocurable resin composition as a photocurable antistatic coating solution. In this case, the transmittance of the high-performance antistatic photocurable resin composition is 3.6%, it can be seen that the high purity SWCNT-Sol in the composition is dispersed in a stable state.

3) Manufacture of Uninterruptible Panel

The high-performance antistatic photocurable resin composition prepared above was flow coated on a polycarbonate sheet (8 cm * 20 cm) having a thickness of 10 mm, and left at room temperature for 1 minute to give flowability (leveling) to flatten the coating surface. After proceeding, put into a forced draft oven heated to 100 ℃ heat treatment for 1 minute, and then UV curing machine irradiated with ultraviolet light at 480 mJ / ㎠ ("RX-C29ud" of Raynix, lamp: 120W / ㎝, high pressure mercury lamp) ) To harden to prepare an antistatic panel having a thin film of the high-performance antistatic photocurable resin composition.

The surface resistance was 2.50 × 10 ⁶ Pa / sq, the transmittance was 90%, and the pencil hardness was 2H.

 Example 2

Except for adding 0.85 parts by weight of p-toluenesulfonic acid (para toluenesulfonic acid) in Example 1 was carried out in the same manner.

The surface resistance was 1.23x10 ⁷ GPa / sq, the transmittance was 91%, and the pencil hardness was 2H.

Example 3

Except for adding 1.2 parts by weight of p-toluenesulfonic acid (para toluenesulfonic acid) in Example 1 was carried out in the same manner.

The surface resistance was 3.25 × 10 ⁸ Pa / sq, the transmittance was 91%, and the pencil hardness was 2H.

Example 4

The same process as in Example 2, except that ethylene glycol (ethylene glycol) was added 0.02 parts by weight based on 100 parts by weight of the prepared acrylate composition.

The surface resistance was 4.80 × 10 ⁷ Pa / sq, the transmittance was 95%, and the pencil hardness was 2H.

Example 5

The same process as in Example 2, except that ethylene glycol (ethylene glycol) was added 0.07 parts by weight based on 100 parts by weight of the prepared acrylate composition. The surface resistance was 8.52 × 10 ⁶ Pa / sq, the transmittance was 95%, and the pencil hardness was 2H.

As a result of the measurement, when ethylene glycol is further added, the surface resistance is remarkably reduced, and the transmittance is improved, indicating that an excellent thin film is formed.

Example 6

Except for the addition of ethylene glycol (ethylene glycol) to 100 parts by weight of the prepared acrylate composition in Example 2, 0.12 parts by weight was carried out in the same manner. The surface resistance was 1.05 × 10 ⁸ Pa / sq, the transmittance was 95%, and the pencil hardness was 2H.

Comparative Example 1

Except for using the surface-modified untreated neat SWCNT with a polymer having a carboxylic acid group in Example 1 was carried out the same.

The surface resistance was 2.04 × 10 ¹³ Pa / sq, the transmittance was 70%, and the pencil hardness was 2H.

In this case, the light transmittance is remarkably lowered, and it can be seen that there is a problem in actual use.

 Comparative Example 2

A high performance antistatic photocurable resin composition was prepared in the same manner as in Example 1 except that no p-toluenesulfonic acid was added.

At this time, the transmittance of the high performance antistatic photocurable resin composition was 100%, and it was found that high purity SWCNT-Sol in the composition aggregated and precipitated, and was not dispersed in a stable state. In addition, SWCNT was deposited on the surface coating layer of the prepared antistatic panel, thereby causing surface defects.

The surface resistance was OVER (immeasurable), the transmittance was 80%, and the pencil hardness was 2H.

In this case, the light transmittance is remarkably lowered, and it can be seen that there is a problem in actual use.

Comparative Example 3

In Example 1, ITO (particle size: 30 nm) was used instead of high purity SWCNT-sol, except that a bead mill (bead size: 0.2 mm) was used to disperse the same. As a result, the surface resistance of 1.70 × 10 ⁷ Ω / sq was realized, but the transmittance was 62%, which was very inferior and could not be used for the purpose of the present invention.

[Comparative Example 4]

3 g of PEDOT (in water / 1% solids / Sooyang Chemtech) was placed in a beaker in 500 ml, and 10 g of 6-functional acrylate DPHA, 3 g of 3-functional acrylate PETA, 3 g of monofunctional acrylate 2-HEMA, and 1.6 g of photoinitiator 18-184 were added thereto. 82.4 g of diluent IPA was added and mixed using a magnetic stirrer. Thereafter, a flow coating was performed on a polycarbonate substrate having a thickness of 10 mm, and then heat-treated in an oven at 100 ° C. for 1 minute after standing at room temperature for 1 minute. The thin film was put into an ultraviolet curing machine irradiated with ultraviolet rays at the final 480 mJ / cm 2. As a result of measuring the surface resistance of the prepared coating surface and the light transmittance, the surface resistance was 9.25 × 10 ⁶ dl / sq, the transmittance was 80%, and the pencil hardness was HB. When UV curing is performed, the surface resistance is significantly increased, and the durability is poor in actual use, and more conductive polymers have to be used to maintain the initial surface resistance. It can be seen that there is a problem.

[Comparative Example 5]

1) Preparation of single-walled carbon nanotubes surface-modified with polymers having carboxylic acid groups

5 g of polyacrylic acid polymer having a weight average molecular weight of 12000 was added to 1 L of n-propanol, and then completely dissolved using ultrasonic waves. 0.5 g of SWCNT (diameter: 1.6 ± 0.6 nm, length: 5 μm or more) was added to the propanol solution, and a mixture was prepared by further mixing for 30 minutes using an ultrasonic wave and a magnetic stirrer. Subsequently, high pressure injection was performed using a high pressure disperser at a pressure of 30,000 psi to obtain SWCNT-Sol.

2) Preparation of antistatic photocurable resin composition

As the photocurable (meth) acrylate monomer composition, 10 g of a 6-functional acrylate Diphentaerythritolhexaacrylate (DPHA), 3 g of a trifunctional acrylate Pentaerythritol triacrylate (PETA) and 3 g of 2-HEMA (2-hydroxyethyl methacrylate) were prepared.

In a beaker prepared separately, 10 parts by weight of the photoinitiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) and 50 parts by weight of isopropyl alcohol based on 100 parts by weight of the photocurable (meth) acrylate monomer composition prepared above. Part was stirred, and 0.5 part by weight was added to the solid content of the prepared SWCNT-Sol, followed by stirring to prepare an antistatic photocurable resin composition.

3) Manufacture of Uninterruptible Panel

After the high-performance antistatic photocurable resin composition was flow coated on a polycarbonate sheet having a thickness of 10 mm, and left at room temperature for 1 minute to give flowability (leveling), and then planarizing the coated surface. After putting it in a forced draft oven heated to 100 ° C and heat-treating for 1 minute, it is cured by putting it in an ultraviolet curing machine (RIX-C29ud, Rays: 120W / cm, high pressure mercury lamp, etc.) irradiated with ultraviolet rays at 480 mJ / ㎠. The final antistatic panel was prepared.

The surface resistance was 1.32 × 10 ¹⁰ Pa / sq, the transmittance was 85%, and the pencil hardness was 1H.

As a result, it can be seen that the surface resistance and pencil hardness are slightly inferior.

Comparative Example 6

The same thing was used in Example 1 except having used polyvinyl alcohol (79% vinylation) of molecular weight 10000 instead of polyacrylic acid. As a result, it was found that the surface resistance was 3.28 × 10 ^7, / sq, and the transmittance was reduced to 70%. Thus, it can be seen that the light transmittance and durability are considerably poor. The pencil hardness was 2B.

Physical property measurement results of Examples and Comparative Examples of the present invention are shown in Table 1 below.

TABLE 1

Claims (11)

An acrylate composition comprising a photocurable polyfunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate oligomer;
Photoinitiators;
Single-walled carbon nanotubes surface-modified with a polymer having a carboxylic acid group;
A high performance antistatic photocurable resin composition comprising at least one function improving agent selected from a compound having a sulfonic acid group and an alkylene glycol; and a solvent,
A high performance antistatic photocurable resin composition having a transmittance of 90% or more and a surface hardness of 1H or more when forming a hard coat film using the high performance antistatic photocurable resin composition. The method of claim 1,
The compound having a sulfonic acid group is any one selected from camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and poly (styrenesulfonic acid) or salts thereof. Or high performance antistatic photocurable resin composition comprising two or more compounds. The method of claim 1,
The acrylate composition is an antistatic photocurable resin composition further comprises a monofunctional (meth) acrylate monomer. The method of claim 1,
The photocurable polyfunctional (meth) acrylate-based oligomer is an antistatic photocurable resin composition comprising a urethane (meth) acrylate-based oligomer. The method of claim 1,
The antistatic photocurable resin composition is 0.01 to 10 parts by weight of a photoinitiator, 0.001 to 2 parts by weight of a single-walled carbon nanotube surface-modified with a polymer having a carboxylic acid group, sulfonic acid group based on 100 parts by weight of the acrylate-based composition High performance antistatic photocurable resin composition comprising 0.1 to 10 parts by weight of the compound having a compound, 0.01 to 10 parts by weight of alkylene glycol and 0.1 to 100 parts by weight of a solvent. The method of claim 1,
The antistatic photocurable resin composition is a high performance antistatic photocurable resin composition further comprises a leveling agent. The method of claim 1,
A high performance antistatic photocurable resin composition further comprising any one or a mixture of two or more selected from conductive polymers or conductive metal particles. An uninterruptible panel having a high-performance antistatic hard coating film formed by coating and curing the antistatic photocurable resin composition of any one of claims 1 to 7 on a surface of a substrate. The method of claim 8,
The high performance antistatic hard coating film is an uninterruptible panel having a surface resistance of less than 10 ^{9 s} / sq. The method of claim 8,
The high performance antistatic hard coating film has a transmittance of 90% or more, the surface hardness is 1H or more uninterruptible panel. Coating an antistatic photocurable resin composition of any one of claims 1 to 7 on a substrate,
Drying step and
UV curing step
Method for producing an uninterruptible panel comprising a.

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