KR102426963B1 - Antistatic Sheet for Photomask Storage Case, Method for Preparing the Same, and Method for Recovering Antistatic Property - Google Patents

Abstract

The present invention relates to an antistatic sheet capable of exhibiting an excellent antistatic function without deterioration in performance by post-processing after manufacture and a method for manufacturing the same. In addition, the present invention is to improve or restore the antistatic function to an area where the antistatic property is reduced or lost by subsequent processing such as cutting or cutting in the process of processing an antistatic treated article into a product such as a photo mask storage case. The present invention is prepared by applying an adhesive on a polymer substrate or a processed area, and applying a thermosetting antistatic composition containing a carbon-based antistatic agent, a polyol, and a polyisocyanate. The antistatic sheet and method, according to the present invention, can be used for interior and exterior materials or packaging materials of semiconductors or electronic products sensitive to static electricity and contamination, storage cases for photomasks or pellicles, and the like.

Description

Antistatic Sheet for Photomask Storage Case, Method for Preparing the Same, and Method for Recovering Antistatic Property}

The present invention relates to an antistatic sheet for a photomask storage case, a manufacturing method thereof, and a method for recovering antistatic properties.

In the manufacture of electronic products such as displays or semiconductors, generation of static electricity or contamination by particulates may cause problems such as malfunction of equipment and product defects. For example, when dust adheres to the photomask, since the dust blocks or reflects ultraviolet light, there is a problem that the transferred pattern is deformed, short-circuited, and the like, resulting in deterioration of quality.

Accordingly, it is necessary to minimize the damage caused by product defects due to static electricity being generated in the working environment, packaging, and transportation process or the material being contaminated with contaminants such as particulates. In order to prevent such damage, the case for storing and transporting electronic components such as photomasks and pellicles, and materials such as electronic components or electronic products including semiconductors, and materials such as packaging materials, require an antistatic function.

As a method of imparting an antistatic function, a method of adding an antistatic agent to the surface substrate of a product or coating or attaching an antistatic sheet on the surface of the product is used. However, when an antistatic agent is added, there is a problem in that the surface resistance becomes uneven due to the non-uniform dispersibility of the antistatic agent or the transmittance decreases in a material such as a photomask, in the case of coating or attaching an antistatic sheet , there was a problem in that the antistatic effect was rapidly reduced by subsequent processes such as washing, rubbing, and the like. In addition, in the case of a case storing a photomask or a pellicle, at least a part of the antistatic film is lost during subsequent processing such as cutting and cutting during the manufacture of the case, so that the antistatic function is rapidly reduced or lost. There is a need for a way to restore function again.

An object of the present invention is to exhibit an excellent antistatic function during the manufacturing process without reduction in performance due to subsequent processing such as thermal drying and washing or processing such as cutting and cutting, To provide an antistatic sheet that can be used as a material or packaging material, a storage case for a photomask or a pellicle, and the like, and a manufacturing method thereof.

Another object of the present invention is to improve the antistatic function in the area where the antistatic property is reduced or lost by subsequent processing such as cutting or cutting in the process of processing the antistatically treated article into a product such as a photomask storage case. It provides a way to recover.

According to one aspect of the present invention, (a) applying an adhesive on a polymer substrate to form an adhesive layer; and (b) forming a first antistatic layer by applying a thermosetting antistatic composition containing a carbon-based antistatic agent, a polyol, and a polyisocyanate on the adhesive layer. do.

According to one embodiment of the present invention, the pressure-sensitive adhesive may be selected from acrylic, urethane, or rubber-based pressure-sensitive adhesives.

According to one embodiment of the present invention, the carbon-based antistatic agent may be at least one selected from carbon nanotubes, graphene, and carbon black.

According to one embodiment of the present invention, the polyol may be at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol.

According to an embodiment of the present invention, the polyisocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate. It may be at least one selected from the group consisting of isocyanate, 4,4-methylenebis(cyclohexylisocyanate), trimethylhexamethylenediisocyanate, 1,3-(isocyanatemethyl)cyclohexane, and triphenylmethane triisocyanate.

According to one embodiment of the present invention, the polymer substrate is acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, impact-resistant PMMA resin, styrene-acrylonitrile (SAN) resin, At least one selected from the group consisting of polyethylene terephthalate (PET) resin, polycarbonate (PC resin), and methyl methacrylate-styrene resin (MS resin) may be included.

According to one embodiment of the present invention, the antistatic sheet may be used in a storage case for a photo mask or pellicle, a photo mask, or a pellicle.

According to an embodiment of the present invention, the step (a) comprises (a-1) forming a second antistatic layer containing a polymer resin and a conductive polymer on the polymer substrate, and (a-2) the second It may include applying an adhesive on the antistatic layer to form an adhesive layer.

According to one embodiment of the present invention, step (a-1) may be carried out by coating using a roll of 100 to 150 mesh.

According to one embodiment of the present invention, the conductive polymer may be at least one selected from polyaniline, polypyrrole, polythiophene, polyacetylene, and derivatives thereof.

According to an aspect of the present invention, there is provided a case for storing a photo mask comprising an antistatic sheet manufactured by the manufacturing method.

According to one aspect of the present invention, the method comprises the steps of applying a pressure-sensitive adhesive to a processed area of an antistatically treated article, and applying a thermosetting antistatic coating composition comprising a carbon-based antistatic agent, a polyol, and a polyisocyanate. A method for restoring or improving antistatic properties in a processed area of an antistatic treated article is provided.

According to an embodiment of the present invention, the processed region may be a region obtained by cutting or cutting the antistatic treated article.

According to the manufacturing method of the antistatic sheet according to the present invention, the surface resistivity value is very low, so the antistatic property is excellent, and the mechanical properties are also excellent. An antistatic sheet in which the performance can be maintained may be provided.

In addition, since the manufacturing step of the manufacturing method is easily available, if a processing area with damaged antistatic properties occurs during subsequent processing such as cutting and cutting the antistatic treated article, the manufacturing step is used to It is also possible to improve or restore antistatic properties.

The antistatic sheet of the present invention may be used for materials of electronic components such as photomasks, pellicles, and semiconductors, their storage or transport cases, or antistatic packaging materials.

1 is a cross-sectional view schematically showing a cross-section of an antistatic sheet according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The terminology used in this application is only used to describe specific embodiments and is not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The shape, size, ratio, angle, number, etc. disclosed in the drawings for explaining the embodiment of the present invention are exemplary, and therefore the present invention is not limited by the matters shown in the drawings. Like elements may be referred to by the same reference numerals throughout the specification.

Each feature of the various embodiments of the present invention may be partially or wholly combined or combined with each other, technically various interlocking and driving are possible, and each of the embodiments may be implemented independently of each other or may be implemented together in a related relationship. may be

Throughout the specification, when a part "includes", "contains", or "has" a certain element, it means that other elements may be further included unless otherwise defined.

Terms such as 1st, 2nd, etc. are used to distinguish one component from another component, and the component is not limited by the above-mentioned terms.

When a part of a layer, membrane, etc. is said to be “above/above” or “below/below” another part, it means that the other part It includes not only cases where they are in contact with each other, but also cases where other parts exist in between. Conversely, when a part is said to be “just above/above” or “just below/below” another part, it means that there is no other part in the middle.

Hereinafter, the present invention will be described in more detail with reference to FIG. 1.'

1. Manufacturing method of antistatic sheet

A method of manufacturing an antistatic sheet according to an aspect of the present invention comprises the steps of: (a) applying an adhesive on a polymer substrate 110 to form an adhesive layer 130 ; and (b) forming a first antistatic layer 122 by applying a thermosetting antistatic composition containing a carbon-based antistatic agent, polyol, and polyisocyanate on the adhesive layer 130 .

According to one embodiment, the step (a) comprises the steps of (a-1) forming a second antistatic layer 121 containing a polymer resin and a conductive polymer on the polymer substrate 110, and (a-2) The method may include forming an adhesive layer 130 by applying an adhesive on the second antistatic layer 121 .

Step (a-1): Formation of the second antistatic layer 121

In step (a-1), the second antistatic layer 121 may be formed by applying an antistatic composition containing a polymer resin and a conductive polymer on the polymer substrate 110 .

The application of the antistatic composition may be performed by applying the composition to the polymer substrate 110 and then drying and heat treatment. In the drying step, the solvent is removed, and the thermosetting resin can be cured by the heat treatment step. The heat treatment may be performed under normal pressure or under pressure. The drying temperature, drying time, heat treatment temperature, heat treatment time, pressurization pressure, etc. may be appropriately selected by those skilled in the art in consideration of the type and content of the components used.

Alternatively, the second antistatic layer 121 may be prepared as a second antistatic sheet in a separate device and then laminated on the above-described polymer substrate 110 under pressure.

At least a part of the second antistatic layer 121 may be removed by cutting or cutting of the product or may be omitted if necessary. It is preferable from the viewpoints of. However, when only the second antistatic layer 121 is laminated alone on the base polymer sheet to form an antistatic sheet, a series of subsequent processes following lamination of the second antistatic layer 121, for example, heat treatment, washing Antistatic properties may decrease during performance of subsequent processes such as, for example. The present inventors laminated the adhesive layer 130 and the first antistatic layer 122 on the second antistatic layer 121, and through this, it was possible to at least reduce the problem of deterioration of antistatic properties due to subsequent processes or processing.

On the other hand, according to one embodiment of the present invention, it may further include the step of preparing the polymer substrate 110 before the step (a-1), the polymer substrate 110 is a thermoplastic resin or thermoplastic to be described later. A mixture of the resin and the thermoplastic elastomer can be produced by extruding, for example, in an extruder.

In addition, according to one embodiment of the present invention, each step in the manufacturing method of the present invention may be made as a continuous process (ie, in-line process). Accordingly, the second antistatic layer 121 of step (a-1) may be formed at the same time as preparing the polymer substrate by extrusion.

Meanwhile, the application of the second antistatic composition in step (a-1) may be performed using a mesh roll. For example, a mesh roll may be installed in a transport means through which the polymer substrate is extruded and transferred, and the antistatic composition may be applied on the polymer substrate through the mesh roll. As the mesh roll, when a roll of 100 to 150 mesh is used, it is preferable in terms of appropriate thickness and uniformity control of the coating film, uniform dispersion of the antistatic agent, and thus improved antistatic properties. If the roll of 100 to 150 mesh is not used, antistatic protection may not be uniformly performed while staining occurs on the sheet surface.

Each component used in this step will be described in detail as follows.

The polymer substrate 110 may include a thermoplastic resin or a mixture of a thermoplastic resin and a thermoplastic elastomer. In addition, the polymer substrate may have a single-layer structure of a thermoplastic resin layer or a mixed resin layer in which a thermoplastic elastomer is mixed with a thermoplastic resin, or a multi-layer structure, for example, a two-layer structure of two different types of thermoplastic resin layers, the first It may have a three-layer structure of a thermoplastic resin layer, a mixed layer of a thermoplastic resin and a thermoplastic elastomer, and a second thermoplastic resin layer. The thickness of the polymer substrate 110 may vary depending on the product to which the antistatic sheet 10 is attached.

According to one embodiment, the polymer substrate 110 is preferably a sheet of a thermoplastic resin having transparency. Examples of the thermoplastic resin include acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, impact-resistant PMMA resin (a resin in which impact resistance is imparted to PMMA by using, for example, an elastic rubber), styrene -Acrylonitrile (SAN) resin, polyethylene terephthalate (PET) resin, polycarbonate (PC resin), methyl methacrylate-styrene resin (MS resin), etc. can be used. According to one embodiment, the polymer substrate comprises at least one selected from the group consisting of ABS resin, PMMA resin, impact-resistant PMMA resin, SAN resin, PET resin, PC resin, and MS resin, or selected from the group It may be composed of one type. According to another embodiment, the polymer substrate may include at least one selected from the group consisting of an ABS resin, a PMMA resin, an impact-resistant PMMA resin, a PET resin, and a PC resin. The thermoplastic elastomer, which may be further added to the sheet of the thermoplastic resin as needed, is a plastic having excellent flexibility and elasticity, and is a polymer material that exhibits rubber elasticity under use conditions but can be molded like a thermoplastic plastic under molding conditions. Examples of the thermoplastic elastomer include a urethane-based resin.

The polymer resin contained in the second antistatic composition may be a thermosetting resin. Specifically, the polymer resin may be at least one selected from the group consisting of acrylic resins, urethane-based resins, urethane-acrylic copolymers, ester-based resins, ether-based resins, amide-based resins, and epoxy-based resins. Alternatively, the polymer resin may use the same resin as the resin used for the polymer substrate, for example, an ABS resin or a PMMA resin.

The conductive polymer contained in the second antistatic composition is a conductive polymer having an antistatic function. The conductive polymer may be at least one selected from polyaniline, polypyrrole, polythiophene, polyacetylene, and derivatives thereof. Examples of the derivative include poly(3,4-ethylenethiophene) and polyethylenedioxythiophene. When polythiophene is used as the conductive polymer, sufficient resistance can be obtained even with a small amount, which is economical. The conductive polymer may be used in an amount of 1 to 500 parts by weight, 20 to 200 parts by weight, or 50 to 100 parts by weight based on 100 parts by weight of the polymer resin. Since the conductive polymer is positively charged in some cases, it may be preferably used in combination with a polymer having an organic acid anion or a non-polymeric organic acid to form an ion pair that balances the positive charge. Examples of such organic acid anions include sulfonate, carboxylate, phosphate, phosphonate, and acrylate. Examples of polymers or non-polymeric organic acids that can be used in combination with the conductive polymer include polystyrenesulfonic acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), polyacrylic acid, polymethacrylic acid, polymaleic acid. , acetic acid, p-toluenesulfonic acid, camphorsulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.

The second antistatic composition may further contain a solvent for the purpose of improving applicability, etc., as long as the solvent does not have a problem with compatibility with other components and does not impair the effects of the present invention such as antistatic properties, Any solvent commonly used in the art may be appropriately selected and used. Examples of the solvent include alcohols (methanol, ethanol, isopropanol, butanol, propylene glycol, methoxy alcohol, etc.), ketones (methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc.) , acetate type (methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc.), cellosolve type (methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc.), hydrocarbon type (normal hexane, normal heptane, benzene, toluene, xylene, etc.) may be used, and these may be used alone or in combination of two or more. The content of the solvent is not particularly limited, and may be included in the remaining amount excluding the above-described components. However, when applied to a continuous process (inline coating method), if a large amount of organic solvent is used, there is a risk of explosion in the drying and heat treatment process, so the content is controlled to 10 wt% or less, more preferably 5 wt% or less in the composition do.

Step (a-2) or step (a): Formation of the adhesive layer 130

In steps (a-2) and (a) (when step (a-1) is omitted), the adhesive layer 130 may be formed by applying an adhesive.

The pressure-sensitive adhesive may be selected from acrylic, urethane, or rubber-based pressure-sensitive adhesives. Among the pressure-sensitive adhesives, an acrylic pressure-sensitive adhesive may be used from the viewpoint of durability. The acrylic pressure-sensitive adhesive may be, for example, a (meth)acrylate polymer or copolymer crosslinked by a crosslinking agent, and examples of the crosslinking agent include an isocyanate compound, an epoxy compound, a melamine compound, and the like. According to one embodiment, the adhesive layer may specifically not include an antistatic agent.

(b) step: formation of the first antistatic layer 122

In step (b), the first antistatic layer 122 may be formed by applying a thermosetting antistatic composition containing a carbon-based antistatic agent, polyol, and polyisocyanate on the adhesive layer 130 .

Application of the thermosetting antistatic composition may be performed by applying the composition to the adhesive layer 130 and then heat-treating the composition. Reaction and thermal curing between the polyol and the polyisocyanate may be achieved by the heat treatment step. The heat treatment may be performed under normal pressure or under pressure. The heat treatment temperature, heat treatment time, pressurization pressure, etc. may be appropriately selected by those skilled in the art in consideration of the type and content of the components used. Typically, the heat treatment may be performed at 50 to 100 ℃, the heat treatment time may be 1 minute to 150 minutes.

Each component in the thermosetting antistatic composition will be described in more detail as follows.

The carbon-based antistatic agent may be at least one selected from carbon nanotubes, graphene, and carbon black. The carbon-based antistatic agent may be used in an amount of 1 to 500 parts by weight, 20 to 200 parts by weight, or 50 to 100 parts by weight based on 100 parts by weight of the total of the polyol and polyisocyanate.

Carbon black includes Ketjen Black EC, Ketjen Black 300j, Ketjen Black 600j, Vulcan XC, Vulkan CSX, Denka Black, Acetylene Black, Conductive Furnace Black, etc. However, carbon black has a disadvantage in that it does not have excellent dispersibility and needs to be used in a large amount for the expression of antistatic performance. Carbon nanotubes and graphene are more preferable in that they can exhibit antistatic properties in a smaller amount than carbon black.

A carbon nanotube is a tube-shaped molecule formed by rolling a graphite plate made up of hexagonal rings made of 6 carbons connected to each other. Since the carbon nanotube has excellent rigidity and electrical conductivity, the film hardness is increased and the antistatic function is improved. In addition, since it does not decompose when exposed to ultraviolet rays or heat, the weather resistance is increased. The carbon nanotube is a single-walled carbon nanotube (SWNT) having a single-wall structure. A double wall carbon nanotube (DWCNT) or a multi-walled carbon nanotube (MWNT) having a multi-wall structure may be used, but is not limited thereto. The carbon nanotubes may preferably have a length of 1 to 60 μm and a diameter of 0.1 to 50 nm.

Graphene is graphite in the form of a sheet in which each layer on the surface of graphite oxide is peeled off. More specifically, after oxidizing graphite powder to produce graphite oxide, and then heating the graphite oxide to a high temperature instantaneously, several layers, for example, 1 to 5 layers, on the surface of the graphite oxide generated by oxidation are peeled off, respectively. It becomes a sheet of graphite, which is graphene. According to an embodiment of the present invention, as graphene, mono-layer graphene or few layer graphene, for example, two-layer graphene, three-layer graphene, four-layer graphene, or five-layer graphene can be used Such graphene is economical because it can be obtained from low-cost graphite by a simple method, and has a characteristic that it not only exhibits a very low resistance value compared to carbon nanotubes, but also can change the electrical properties by controlling the crystal orientation. In addition, since graphene has a stable structure, excellent antistatic properties can be maintained even after being left in a high temperature environment, and reflection and scattering of light can be effectively prevented by adjusting the size of the sheet shape, thereby reducing light transmittance can also be prevented. According to an embodiment of the present invention, graphene is graphene in the form of a sheet.

The first antistatic layer 122 may exhibit an excellent antistatic function by containing a carbon-based antistatic agent.

The polyol is an organic compound having two or more plural hydroxyl groups (-OH) in one molecule. Examples of the polyol include polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol. According to one embodiment of the present invention, the polyol may be at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol.

The polyester polyol may be obtained by, for example, an esterification reaction between a polyhydric alcohol component and an acid component. Here, the polyol component may include, for example, ethylene glycol, diethylene glycol, butanediol, glycerin, trimethylolpropane, pentaerythritol, polypropylene glycol, and the like, and the acid component is, for example, succinic acid, methylsuccinic acid, adipic acid acid, pimelic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, and the like. The polyether polyol may be obtained, for example, by addition polymerization of an alkylene oxide to a polyhydric alcohol or the like. Examples of the polycaprolactone polyol include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone. The polycarbonate polyol may be obtained by reacting a polyhydric alcohol component with a carbonate-based compound.

The polyisocyanate is an organic compound having two or more isocyanate groups in one molecule. The polyisocyanate is, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, 4, 4-methylenebis (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, 1, 3- (isocyanate methyl) cyclohexane, triphenylmethane triisocyanate, etc. are mentioned.

The polyol and polyisocyanate may be blended in an equivalent ratio of 1:1 to 1:0.5.

The thermosetting antistatic composition may further contain a solvent. For the solvent, refer to the description of the solvent contained in the composition for the second antistatic layer. Moreover, the said thermosetting type antistatic composition may further contain other additives, such as an initiator, a catalyst, and a stabilizer.

2. Antistatic sheet and products containing the same

According to one aspect of the present invention, there is provided an antistatic sheet manufactured by the above-described manufacturing method.

According to an embodiment, the antistatic sheet 10 includes a polymer substrate 110; an adhesive layer 130 on one or both sides of the polymer substrate 110; and a first antistatic layer 122 containing a carbon-based antistatic agent and a reaction product of a polyol and polyisocyanate on the adhesive layer 130 .

According to another embodiment of the present invention, the antistatic sheet 10 includes a polymer substrate 110; a second antistatic layer 121 containing a polymer resin and a conductive polymer on one or both sides of the polymer substrate 110; an adhesive layer 130 on the second antistatic layer 121; and a first antistatic layer 122 containing a carbon-based antistatic agent and a reaction product of a polyol and polyisocyanate on the adhesive layer 130 .

According to another embodiment of the present invention, the antistatic sheet 10 includes a polymer substrate 110; a second antistatic layer 121 containing a polymer resin and a conductive polymer on one surface of the polymer substrate 110; an adhesive layer 130 on the other surface of the polymer substrate 110; and a first antistatic layer 122 containing a carbon-based antistatic agent and a reaction product of a polyol and polyisocyanate on the adhesive layer 130 .

According to another embodiment of the present invention, the antistatic sheet 10 includes a polymer substrate 110; a second antistatic layer 121 containing a polymer resin and a conductive polymer on both sides of the polymer substrate 110; an adhesive layer 130 on any one of the second antistatic layers 121; and a first antistatic layer 122 containing a carbon-based antistatic agent and a reaction product of a polyol and polyisocyanate on the adhesive layer 130 .

A detailed description of each component constituting the second antistatic layer 121 , the adhesive layer 130 , and the first antistatic layer 122 will be omitted because the content described in the manufacturing method may be referred to. Each of the second antistatic layer 121 and the first antistatic layer 122 may have a thickness in a range of 0.08 to 0.1 μm.

The antistatic sheet 10 according to the present invention may be used for a photomask, a pellicle, a material for electronic components such as semiconductors, a storage case thereof, or an antistatic packaging material. For example, according to an embodiment of the present invention, a photomask storage case including the above-described antistatic sheet of the present invention may be provided.

3. Method of recovery or improvement of antistatic properties

According to one aspect of the present invention, the method comprises the steps of applying a pressure-sensitive adhesive to a processed area of an antistatically treated article, and applying a thermosetting antistatic coating composition comprising a carbon-based antistatic agent, a polyol, and a polyisocyanate. A method for restoring or improving antistatic properties in a processed area of an antistatic treated article is provided.

The antistatic sheet of the present invention may require additional processing treatment. For example, the antistatic sheet is processed in the form of a sheet by extrusion, compression, etc. in various specifications, and can be manufactured in various specifications in the form of a thickness of 5 to 20 mm, a width of ~1200 mm, and a length of ~2400 mm. These sheet-shaped products are processed into various parts through processes such as cutting and cutting. can be lost

The thermosetting antistatic composition containing the carbon-based antistatic agent, polyol, and polyisocyanate used in the method for producing the antistatic sheet of the present invention described above is preferably in a liquid state and at a relatively low temperature, for example, 50 to 100°C. By the heat treatment of the polyol and polyisocyanate react and harden, it is possible to easily form an antistatic layer. However, in the case of areas processed such as cutting and cutting, it may be difficult to form the antistatic layer uniformly and durable. have.

Antistatic properties can be improved or restored by applying an antistatic coating composition after applying an adhesive to the processed area according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the contents of the present invention are not limited by the following examples.

[Example 1]

After coating an antistatic layer containing a conductive polymer on both sides of a polymer substrate using a 100 to 150 mesh roll, an acrylic adhesive is applied thereon, and then an antistatic coating composition containing graphene, polyol and polyisocyanate is applied and heat treatment at 60 to 80° C. to prepare an antistatic sheet.

[Comparative example]

The antistatic sheet prepared in Example 1 was washed and cut.

[Example 2]

After applying the acrylic adhesive on the cut-treated area in the antistatic sheet of Comparative Example, an antistatic coating composition containing graphene, polyol and polyisocyanate was applied and heat-treated at 60 to 80°C.

[Experimental Example] Measurement of surface resistance

The surface resistance of the antistatic sheets of Examples 1 and 2 and Comparative Example was measured using the apparatus and method shown in [Table 1] below, and the results are shown in [Table 2] below.

measuring instrument Measurement method and measurement conditions

SIMCO ST-4 Surface Resistance Measurement

Measuring range
10E13 Ω/□ (or Ω) at 10³
measurement environment
15 ℃ ~ 25 ℃, 60% RH or less
electrode material
Special conductive rubber (volume resistance 0.02 Ω·cm MAX)
Measurement precision
Exponential display value ± 0.5 (exponent) (eg 10E8.5 , 10E0.5 )
Measured voltage
automatically switch voltage
① 3rd to 6th: 10V, 10mA max
② 6th to 13th: 100V, 1mA max

Example 1 comparative example Example 2 Average surface resistance value 10E5.7 Ω~10E7 Ω 10E13.5 Ω 10E6 Ω~10E7.5 Ω

Although the preferred embodiment of the present invention has been described in detail above, the above-described embodiment is presented as a specific example of the present invention, and the present invention is not limited thereto. Various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in are also within the scope of the present invention.

10: antistatic sheet
110: polymer substrate
121: second antistatic layer 122: first antistatic layer
130: adhesive layer

Claims (13)

(a-1) forming a second antistatic layer by applying an antistatic composition containing a polymer resin and a conductive polymer on a polymer substrate using a mesh roll;
(a-2) forming an adhesive layer by applying an adhesive on the second antistatic layer; and
(b) forming a first antistatic layer by applying and heat-treating a thermosetting antistatic composition containing a carbon-based antistatic agent, polyol, and polyisocyanate on the adhesive layer,
In step (a-1), the polymer substrate is acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate (PMMA) resin, impact-resistant PMMA resin, styrene-acrylonitrile (SAN) resin, polyethylene At least one selected from the group consisting of terephthalate (PET) resin, polycarbonate (PC resin), and methyl methacrylate-styrene resin (MS resin),
The polymer resin is at least one selected from the group consisting of an acrylic resin, a urethane-based resin, a urethane-acrylic copolymer, an ester-based resin, an ether-based resin, an amide-based resin, and an epoxy-based resin, or the same as the resin used in the polymer substrate Suzy,
A method for manufacturing an antistatic sheet for manufacturing a storage case for a photomask or pellicle. According to claim 1,
The pressure-sensitive adhesive is selected from acrylic, urethane-based, or rubber-based pressure-sensitive adhesives, the method. According to claim 1,
The method of claim 1, wherein the carbon-based antistatic agent is at least one selected from carbon nanotubes, graphene, and carbon black. According to claim 1,
The polyol is at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol. According to claim 1,
The polyisocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, 4,4-methylenebis (Cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, 1,3- (isocyanate methyl) cyclohexane, and at least one selected from the group consisting of triphenylmethane triisocyanate, the method. delete delete delete According to claim 1,
The (a-1) step is carried out by applying using a roll of 100 to 150 mesh, the method. According to claim 1,
The method, wherein the conductive polymer is at least one selected from polyaniline, polypyrrole, polythiophene, polyacetylene, and derivatives thereof. A case for storing a photo mask manufactured by processing the antistatic sheet manufactured by the manufacturing method according to claim 1 . delete delete

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