KR20110020139A - Photo curable antistatic coating composition having metal salt compound - Google Patents

Abstract

PURPOSE: A photo-curable antistatic coating composition is provided to impart excellent antistatic properties of surface resistance of 10^8-10^11 ohm/area to the surface of a film and object and to ensure high washing resistance to a solvent. CONSTITUTION: A photo-curable antistatic coating composition includes a photo-curable resin and a metal salt compound as active ingredients. The photo-curable resin includes a monomer or oligomer where alkylene oxide group introducing an alkyloxide group is present at one side and photo-curable alkyloxide or metacrylate functional groups are present at the other side.

Description

Photo curable antistatic coating composition having metal salt compound

The present invention relates to a photocurable (or ultraviolet curable) resin composition comprising an antistatic material (IDP) made of a metal salt, and more particularly, to a component containing oxygen such as methylene oxide or ethylene oxide. The present invention relates to a resin composition composed of an alkyl oxide such as ethyl oxide or methyl oxide at one end of a main chain, and more preferably a metal salt compound to a resin into which an acrylate or methacrylate group capable of UV curing is introduced at the other end. It relates to a resin composition prepared by mixing.

Semiconductors, liquid crystal displays, or various electronic products are transported using antistatic film or in an antistatic container to prevent electrostatic damage that may occur in various stages of manufacturing, transportation, and handling. Should be.

There are several types of antistatic agents used for antistatic purposes, including conductive carbon blacks, surfactant type antistatic agents, ionic liquids, inherently conductive polymers (ICP), or metal salt compounds. There are several types of antistatic agents (inherently dissipative polymers; IDP). Each of these components is mixed with a binder component such as urethane or acrylic in the case of a film to form an antistatic layer on the surface of the film, so that these surface antistatic layers effectively dissipate or dissipate static electricity generated from the outside or from the component, and It serves to protect electrical components and devices from static damage.

However, each of these components has advantages and disadvantages, and thus many restrictions on use. For example, when the conductive carbon black is used, the antistatic property is quite good, but when the antistatic layer formed on the surface is dropped during handling, the conductive foreign material acts to conduct the component, which causes the component to be severely damaged. . Although the conductive carbon black is surrounded by an organic binder, the conductivity of the conductive carbon black is so high that when it is placed in the middle of the circuit of the component, the leakage current between circuits increases, which leads to the conduction of the component. This is because it causes destruction damage.

Surfactant type antistatic agents used in the past have been widely used since they are transparent, easy to mix with a polymer material, and transparent when coated on a surface. However, since these surfactant type antistatic agents have humidity dependence, when the relative humidity is higher than 50%, the surface resistance can be up to about 10 ¹⁰ ohms / area, but when the relative humidity is 20-30% or less, the electrical conductivity is lost. Many months after the formation of the antistatic layer, there are many disadvantages, such as the antistatic properties disappear, so that it is rarely used in recent years.

Ionic liquids are compounds that contain ions and can even have surface resistances of up to 10 ⁹ ohms / area.In case of film-type antistatic products, 1-10 parts by weight of a photocurable acrylate resin is mixed. 10 ¹⁰ ohm / area surface resistance is also available. In addition, the use of an ionic liquid having good compatibility with the photocurable acrylate resin prevents the antistatic property from disappearing, and thus has been widely used for providing antistatic properties of films.

However, this material is not suitable for long-term reliability test when it is used with a photocurable resin composition, and eventually causes a problem of crawling to the surface, applying temperature and humidity.

In order to overcome the above-mentioned disadvantages, the conductivity is lower than the conductive carbon black, but conductive polymers (conducting polymers), which are materials that can be sufficiently used as an antistatic agent, are used. The conductive polymer is an organic polymer whose material itself has electrical conductivity. Representative conductive polymers include polypyrrole, polyaniline, polythiophene, and modified conductive polymers derived therefrom. This material has a lower electrical conductivity than the conductive carbon black, which can suppress breakage damage caused by energization. A typical conductive polymer that is currently commercialized is poly (3,4-ethylenedioxythiophene) (PEDOT), a conductive polymer of HC Starck (Grade: Clevious P). The conductive polymer is mainly sold in the form of dispersed in water, and it is well mixed with a water-soluble organic binder to form an antistatic coating solution and then coated on the surface of the coating agent to form an antistatic layer to prevent the static damage.

However, as described above, as the degree of integration of circuits increases, the gap between circuit patterns decreases, and when the antistatic layer material made of conductive polymer is dropped and interposed between circuit patterns, the leakage current between the patterns may increase, which may cause breakage damage by energization. have.

In general, an antistatic coating using a conductive polymer uses an antistatic layer containing a conductive polymer as an active ingredient to form an antistatic layer to have 10 ⁶ ohms / area on the surface of films. In this case, the surface resistance of the surface layer is 10 ⁶ ohms / area, but substantially 10 ⁴ ohms / area is a shape in which conductive polymer components are piled up by an organic insulator organic binder. Therefore, if the antistatic layer of the surface layer is dropped and placed between the circuit patterns, there is a high possibility that there is a portion of 10 ⁴ ohms / area rather than 10 ⁶ ohms / area, which is the resistance of the coating surface. If there is a part that shows a high electrical conductivity, this partly increases the leakage current, which eventually leads to breakage damage caused by energization.

In addition, if an antistatic material is formed in the antistatic layer, this antistatic performance should be maintained for a long time (permanent antistatic), and the humidity dependence should not be large, especially over time. In addition, as described above, in order to suppress breakage damage caused by an increase in leakage current, the electrical conductivity of the material itself should be as low as possible. That is, in the case of surface resistance, the surface resistance should be as high as possible while maintaining the permanent antistatic property. In general, when an antistatic coating is formed on the surface of the film, a surface resistance of about 10 ^{9-10 10} ohms / area is sufficient as antistatic or antistatic property.

An antistatic compound which can satisfy the above conditions and is easily mixed with an organic binder is a method using a metal salt compound. This metal salt compound is a compound which mainly uses metals, such as lithium or sodium as a cation, and consists of various organic and inorganic compounds with an anion. When the compound is mixed with a compound containing oxygen such as ethylene glycol to form a composition, it can be used as a permanent antistatic agent. This mixture is mixed with a urethane-based or amide-based elastomer and is widely used as an antistatic composition for thermoplastic resins.

As a representative example, these mixtures, i.e., lithium salt compounds, ethylene glycol, urethane-based elastomers, etc. are mixed in a certain amount and mixed with a polyester copolymer (PETG; polyethyleneterephthalate copolymer), which is a representative thermoplastic polymer, to make a flat sheet, which is very good antistatic. It is possible to produce a polymer sheet showing the properties. This technology is currently used as an antistatic sheet for the manufacture of head stack assemblt (HSA) packagings, the electronic components requiring the highest antistatic performance.

As described above, it is very effective to impart the antistatic property of the thermoplastic resin using the antistatic agent containing a metal salt compound which is a permanent antistatic agent and does not have high electrical conductivity by itself and thus does not have a high risk of leakage current. In addition, when mixed with a lithium salt compound and ethylene glycol and a urethane-based elastomer, the antistatic component is an extremely useful antistatic material having the advantage of not only having antistatic property but also not being transferred to the surface, and in particular, the antistatic property is permanently maintained.

However, when a photocurable antistatic composition prepared by mixing an antistatic agent containing the metal salt compound into a photocurable or ultraviolet curable resin composition is used as a photocurable antistatic material, the surface resistance of the antistatic layer is rapidly increased after photocuring. There is a problem of losing the antistatic property is a big constraint on the application.

As described above, when the metal salt compound is mixed with ethylene glycol and a urethane-based compound, it provides effective antistatic properties to the thermoplastic resin, but when a similar composition is mixed with a photocurable acrylate resin system having a urethane group, photoconversion loses electrical conductivity. There is a disadvantage that the prevention performance is sharply lowered.

Therefore, there is a need for the invention of a photocurable resin composition containing a new metal salt compound which does not have a phenomenon of rapidly increasing surface resistance during photocuring after mixing with an acrylate resin while using a metal salt compound as an antistatic agent component.

In order to solve the above problems, an object of the present invention is a photocurable resin composition containing a metal salt compound as an active ingredient, a new photocurable resin composition containing a metal salt compound whose surface resistance does not rapidly increase even after photocuring. To provide.

In order to achieve the above object, the photocurable antistatic resin composition of the present invention contains a photocurable resin such as a monomer or oligomer having an alkylene oxide group and a metal salt compound as active ingredients.

One end of the monomer or oligomer having an alkylene oxide group may be substituted with an alkyl oxide, and the alkyl oxide may be any one of methyl oxide, ethyl oxide, propyl oxide, butyl oxide, and the like.

Also preferably, in the photocurable antistatic resin composition according to the present invention, photocurable resins and metal salts such as alkylene oxide monomers or oligomers, one end of which is substituted with an alkyl oxide and the other end of which is an acrylate or methacrylate. It is to include as an active ingredient.

In addition, the metal salt may be used by mixing any one or more of lithium salt, sodium salt and potassium salt.

The inventors of the present invention, in the study of permanent antistatic photocurable resin composition, when a permanent antistatic agent prepared by mixing a metal salt compound such as a lithium salt with a compound containing oxygen such as ethylene glycol and photocured by mixing with a general photocurable resin It was confirmed that a phenomenon in which the surface resistance suddenly increased and the antistatic property rapidly lost.

In the case of general thermoplastic resins, when mixed with a metal salt compound and ethylene glycol and a urethane-based elastomer, 10 ⁸ -10 ¹⁰ ohms / area has a very good surface resistance as an antistatic agent. Therefore, the urethane-based acrylate resin is expected to have the same effect instead of the urethane elastomer, so the urethane-based acrylate resin is mixed with the antistatic agent prepared by mixing a metal salt compound and ethylene glycol, but photocuring as described above. After that, the surface resistance was increased sharply and increased to more than 10 ¹¹ ohms / area, thus losing the antistatic property. In addition, it was found that most urethane-based photocurable resins exhibit all these characteristics.

In order to overcome this problem, in the present invention, a monomer or oligomer having an alkylene oxide is used in a unit containing oxygen, and an alkyl oxide group is introduced at one side thereof. More preferably, a monomer or oligomer type photocuring resin (hereinafter referred to as alkylene oxide resin) composed of acrylate or methacrylate which is photocurable is used as the other side of the monomer or oligomer. The alkylene oxide resin may be described in more detail by the following Chemical Formula 1 or 2 as an example,

In formulas (1) and (2), R means alkyl, and the opposite side refers to a monomer or oligomeric photocurable resin composed of acrylate or methacrylate.

That is, a metal salt compound was directly mixed with the alkylene oxide resin to prepare an antistatic photocurable resin composition.

The metal salt compounds that can be used in the present invention are lithium salts, sodium salts and potassium salts, and representative metal salt compounds include lithium perchlorate (LiClO ₄ ), sodium perchlorate (NaClO ₄ ), potassium perchlorate (KClO ₄ ), and lithium hexafluoroalcene. Nate (LiASF ₆ ), Lithium tetrafluoroborate (LiBF ₄ ), Lithium hexafluorophosphate (LiPF ₆ ), Lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), Bis (trifluoromethanesulfonyl) Drithium (LiN (CF ₃ SO ₂ ) ₂ ), tris (trifluoromethanesulfonyl) methedritium (LiC (CF ₃ SO ₂ ) ₃ ), and the like. In particular, LiClO ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiAsF ₆ , LiI, LiBr, LiSCN, LiSO ₃ CF ₃ , LiNO ₃ , LiC (SO ₂ CF ₃ ) ₃ , Li ₂ S and LiMR ₄ ( Herein, a lithium salt compound such as M is Al or B, and R is a halogen, alkyl or aryl group) is useful, and two or more kinds thereof may be mixed and used.

The alkali metal salt compound is a material that exhibits ion conduction by ion dissociation. If the content of the alkali metal salt compound is too small, the antistatic performance is decreased. If the alkali metal salt compound is too large, the increase of the antistatic performance is slowed, and the thermal stability of the metal salt is poor, which may cause material deterioration. It is preferable to use between 0.05-20% by weight.

At this time, if necessary, the metal salt compound may be used by mixing in a suitable solvent. In this case, the solvent content or the solid content does not have a particular range, and the solvent amount may be determined as necessary. If necessary, the metal salt compound may be directly mixed with the acrylate resin without using a solvent. The solvent which can be used at this time can use any solvent as long as it can melt | dissolve a metal salt compound and is compatible with photocurable resin. Typical solvents include alcohol solvents such as ethyl acetate, methyl alcohol, ethyl alcohol and isopropyl alcohol, ethylene glycol, glycerol, benzene, chlorobenzene, nitromethane, toluene, hexane, cyclohexane, xylene, chloroform, tetrahydrofuran, Dimethylformamide, acetonitrile, methylethylketone, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylformamide, dimethyl sulfoxide, acetone, n -Any one of solvents such as an organic solvent such as butyrolactone, or the like may be used in combination. In addition, when using a bipolar solvent when mixed with the photocurable resin, an aqueous solvent such as water can also be used.

As described above, the photocurable resin composition of the present invention can be used as a general transparent permanent antistatic coating as well as suppressing breakage damage caused by an increase in leakage current. For example, when the resin composition of the present invention is applied to the surface of a general injection molded product prepared by injection molding, and then photocured to form an antistatic layer, an antistatic layer having strong solvent resistance to solvents such as water or alcohol may be formed. . In this case, the photocurable resin composition may be used as it is or in a diluted state by mixing in a suitable solvent. Further, the antistatic layer coating method may be various methods that can be applied to the surface of the injection molding, such as an impregnation method and a spray coating method. As such, the photocurable antistatic resin composition may have a surface resistance of 10 ⁸ -10 ¹¹ ohms / area after being used as a coating and photocuring.

In addition, the antistatic resin composition of the present invention may be prepared directly into an object product to make an antistatic product or by applying the resin composition to an object to be coated to prepare an antistatic product.

When the resin composition is prepared by using the photocurable (or ultraviolet curable) resin composition containing the metal salt proposed in the present invention and coated on the surface of the film or the coated object, the surface resistance is 10 ^{8-10 11} ohms / area. Antistatic products can be produced that exhibit stable antistatic properties. In particular, the antistatic film (or antistatic product) according to the technique of the present invention can form a good permanent antistatic layer with no change over time without being wiped with water or alcoholic solvents.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are only examples for describing the present invention and do not limit the scope of the present invention.

Property measurement

Five items of surface resistance, friction voltage, decay time, washability, and long-term reliability were measured to prove the effect of the present invention. The measurement method of each item is as follows.

Surface resistance: The resin composition was apply | coated to a polyester film, and then photocured and the specimen was produced. The surface resistance of the resin composition was measured according to the method of ESD STM 11.11 using ST-3 of Shimko, Japan.

Friction voltage: The resin composition was applied to a polyester film and then photocured to prepare a specimen. After wearing nitrile gloves on the coated surface, rubbing vigorously ten times, the electrostatic voltage generated on the surface was measured according to the ESD STM 11.2 method using FMX-003 manufactured by Shimko, Japan.

Decay time: The resin composition was applied to a polyester film and then photocured to prepare a specimen. The coated surface was measured according to FTMS 101C method using CPM288 of Monroe Electronics.

Washability: The resin composition was applied to a polyester film and then photocured to prepare a specimen. The prepared specimens were washed 10 times with distilled water and dried to observe the change in resistance.

Long-term reliability: The resin composition was applied to a polyester film and then photocured to prepare a specimen. The prepared specimen was left at 25 degrees 45% RH to observe the change in resistance after one month.

Comparative Example 1

0.1 g of lithium bis (trifluoromethanesulfonyl) imide, 1 g of urethane acrylate-based photocurable oligomer, and 1 g of monomer are dissolved in ethyl acetate at 30% by weight, followed by further dissolving 0.2 g of photoinitiator. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

Comparative Example 2

After dissolving 1 g of ethylene oxide-based photocurable oligomer and 1 g of monomer in 30% by weight in ethyl acetate, 0.2 g of photoinitiator is further dissolved. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

Comparative Example 3

0.5 g of quaternary ammonium-based antistatic agent, 1 g of ethylene oxide-based photocurable oligomer, and 1 g of monomer are dissolved in ethyl acetate at 30% by weight, and then 0.2 g of photoinitiator is further dissolved. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

<Comparative Example 4>

0.5 g of 1-butyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide, a kind of ionic liquid, and 1 g of ethylene oxide-based photocurable oligomer and 1 g of monomer were dissolved in ethyl acetate at 30% by weight. After that, 0.2 g of photoinitiator is further dissolved. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

&Lt; Example 1 >

0.03 g of lithium bis (trifluoromethanesulfonyl) imide, 1 g of ethylene oxide-based photocurable oligomer and 1 g of monomer are dissolved in ethyl acetate at 30% by weight, followed by further dissolving 0.2 g of photoinitiator. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

<Example 2>

0.1 g of lithium bis (trifluoromethanesulfonyl) imide, 1 g of ethylene oxide-based photocurable oligomer, and 1 g of monomer are dissolved in ethyl acetate at 30% by weight, followed by further dissolving 0.2 g of photoinitiator. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

<Example 3>

0.2 g of lithium bis (trifluoromethanesulfonyl) imide, 1 g of ethylene oxide-based photocurable oligomer and 1 g of monomer are dissolved in ethyl acetate at 30% by weight, followed by further dissolving 0.2 g of photoinitiator. The prepared solution was applied to a polyester film, dried at 80 ° C. for 1 minute, and then UV cured at 300 mJ. The physical properties of the produced film are shown in Table 1.

<Example 4>

The solution prepared in Example 1 was applied to a pre-injected 48-inch LCD backlight unit tray by a spray method, dried at 80 ° C. for 1 minute, and then UV-cured at 300 mJ. Physical properties of the coated trays are shown in Table 1.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Surface Resistance (Ω / sq) > 1E12 > 1E12 1E10 5E10 1E10 2E9 7E8 2E10 Friction Voltage (V) 3000 2700 300 500 300 200 150 300 Decay time (s) > 100 > 100 3 5 3 One <0.1 3 Cleanability (Ω / sq) > 1E12 > 1E12 > 1E12 > 1E12 2E10 3E9 8E8 3E10 Long term reliability (Ω / sq) > 1E12 > 1E12 > 1E12 > 1E12 1E10 3E9 6E8 2E10

Claims (5)

In the photocurable antistatic resin composition, the composition, On one side, an alkylene oxide group having an alkyl oxide group introduced thereon, and on the other side, a photocurable resin comprising a monomer or oligomer having an acrylate or methacrylate functional group capable of photocuring, and a metal salt compound, comprising as an active ingredient Photocurable antistatic resin composition. The photocurable antistatic resin composition according to claim 1, wherein the metal salt is used by mixing any one or more of lithium salt, sodium salt and potassium salt. The photocurable antistatic resin composition according to claim 2, wherein the content of the metal salt is 0.05-20% by weight relative to the total resin composition. The photocurable antistatic resin composition according to claim 2, wherein the photocurable antistatic resin composition is used as a coating agent and has a surface resistance of 10 ⁸ -10 ¹¹ ohms / area after photocuring. An antistatic product prepared directly from the antistatic resin composition of claim 1 or coated with the resin composition and subjected to an antistatic treatment.