KR102525523B1 - Electromagnetic wave shielding binder resin, electromagnetic wave shielding coating composition including the same, and electromagnetic wave shielding film formed therefrom - Google Patents

Abstract

(상기 화학식 1에서, M은 금속칼코겐 화합물이고, R₁은 C2~C6 치환 또는 비치환된 알킬렌기, R₂는 수소 또는 메틸(CH₃)이다)The present invention relates to a binder resin for electromagnetic wave shielding capable of forming a shielding film capable of realizing homogeneous electromagnetic wave shielding properties with excellent initial and long-term dispersion stability, and a coating composition for electromagnetic wave shielding including the same. More specifically, (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) saturated diacid compound and hydroxy (C2-C4) alkyl (meth) acrylate Regarding a binder resin for electromagnetic wave shielding polymerized including a monomer prepared by condensation of (d) cyclo(C3-C6)alkyl(meth)acrylate and (e) (meth)acrylate represented by Formula 1 below will be.
[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

Description

A binder resin for electromagnetic wave shielding, a coating composition for electromagnetic wave shielding comprising the same, and an electromagnetic wave shielding film formed therefrom

The present invention relates to a binder resin for electromagnetic wave shielding, a coating composition for electromagnetic wave shielding comprising the same, and an electromagnetic wave shielding film formed therefrom.

Electromagnetic waves are generated by the operation of electronic components, and these electromagnetic waves are high-frequency, and malfunctions of electronic devices are becoming a problem due to electromagnetic wave interference, and health problems of users are also emerging.

As a method for shielding these electromagnetic waves and electromagnetic interference (EMI), a shielding conductor can has been conventionally used, but in recent years, due to high integration of electronic devices such as semiconductor parts, conductor cans have been replaced. A method of directly covering a surface of an electronic component or PCB with a conductive film has been proposed.

Two methods, sputtering and spraying, are proposed as alternative methods for directly covering a conductive film on a part. In the case of sputtering, a thin conductive film is coated on the surface of a target, so its electrical properties and mechanical properties are not excellent. However, in the case of a three-dimensional three-dimensional structure, the conductive film deposited on the vertical surface is significantly thinner than the conductive film deposited on the horizontal surface, greatly reducing the shielding effect. In addition, the process cost is very expensive and takes a long time, resulting in a large amount of It had the disadvantage of being unsuitable for production.

On the other hand, in spraying, a conductive liquid, which is a heterogeneous compound in which conductive powders are mixed with liquid resin, is sprayed on the surface of a target by spraying and then hardened to form an EMI shielding film. is to make In general, copper, silver, nickel, or graphite is used as a conductor, and epoxy, acrylic, urethane, or rubber is used as a resin. The spraying method has the advantage of being suitable for mass production as the time required for the process is very short and the process unit cost is very low. there is.

Accordingly, there is a need for a new coating composition for electromagnetic wave shielding capable of achieving uniform dispersion stability of conductor powder and forming a homogeneous conductor film by spraying.

Korea Patent Registration No. 10-0704243 (2007.03.30.)

An object of the present invention is to provide a binder resin for electromagnetic wave shielding capable of realizing excellent dispersion stability for a long time and a coating composition for electromagnetic wave shielding comprising the same. More specifically, (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) saturated diacid compound and hydroxy (C2-C4) alkyl (meth) acrylate By including a polymerized binder resin including a monomer prepared by condensation of (d) cyclo (C3-C6) alkyl (meth) acrylate and (e) (meth) acrylate represented by Formula 1 below, When forming a coating composition in which a conductive filler having a high specific gravity such as powder is mixed, a homogeneous mixture in which the conductive filler is uniformly dispersed can be realized, and an electromagnetic wave shielding coating composition capable of implementing excellent dispersion stability for a long period of time is provided. . In addition, it is an object of the present invention to provide a coating composition for electromagnetic wave shielding that has excellent ejectability and is suitable for forming an electromagnetic wave shielding film by spraying.

[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

Another object of the present invention is to provide an electromagnetic wave shielding film having excellent heat resistance, transparency, high water contact angle (DW), cross-cut characteristics, and pencil hardness of 3H or more by providing a coating composition for electromagnetic wave shielding containing the above-described binder resin. .

The binder resin for electromagnetic wave shielding of the present invention for achieving the above object is (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) saturated diacid compound and hydroxy Monomer prepared by condensation of hydroxy (C2-C4) alkyl (meth) acrylate, (d) cyclo (C3-C6) alkyl (meth) acrylate and (e) (meth) acrylate represented by the following formula (1) It is characterized by being polymerized, including.

[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

In the binder resin for electromagnetic wave shielding according to an embodiment of the present invention, the metal of the metal chalcogen compound is any one or two or more metals selected from the group consisting of Mo, W, Sn, Bi and Sb, and the metal chalcogen The chalcogen of the compound may be any one or two or more elements selected from the group consisting of S, Se and Te.

In the binder resin for electromagnetic wave shielding according to an embodiment of the present invention, the saturated diacid compound may be at least one selected from succinic acid, malic acid, adipic acid, and glutaric acid.

The present invention includes a coating composition for electromagnetic wave shielding including the above-described binder resin for electromagnetic wave shielding, a conductive filler, and a diluent.

In the coating composition for electromagnetic wave shielding according to an embodiment of the present invention, the conductive filler is at least one selected from metal particles, metal salts, conductive polymers, carbon particles, carbon tubes, carbon nanotubes, graphene, and graphene oxide. It may contain ingredients.

In the coating composition for shielding electromagnetic waves according to an embodiment of the present invention, the composition includes 10 to 70% by weight of the conductive filler, 5 to 50% by weight of the binder resin for shielding electromagnetic waves, and 20 to 80% by weight of a diluent. can

In the coating composition for shielding electromagnetic waves according to an embodiment of the present invention, the coating composition for shielding electromagnetic waves may have a dispersion stability index (TSI) of less than 3.5 for 45 hours.

In the coating composition for shielding electromagnetic waves according to an embodiment of the present invention, the coating composition for shielding electromagnetic waves may have a change rate of less than 1.5 in a dispersion stability index (TSI) after 3.5 hours from the initial level.

The present invention includes an electromagnetic wave shielding film including the above-described binder resin for electromagnetic wave shielding.

The electromagnetic wave shielding film according to an embodiment of the present invention may have a pencil hardness of 3H or more.

The electromagnetic wave shielding film according to an embodiment of the present invention may have crosscut 4B or higher according to the ISO 2409 standard.

The electromagnetic wave shielding film according to an embodiment of the present invention may have a water contact angle of 50 degrees or more.

The electromagnetic wave shielding film according to an embodiment of the present invention may have electrical conductivity of 60 mΩ/10 μm or less.

The coating composition for shielding electromagnetic waves according to the present invention includes (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) a saturated diacid compound and hydroxy (C2-C4) Monomers prepared by the condensation of alkyl (meth) acrylates, (d) cyclo (C3-C6) alkyl (meth) acrylates, and (e) electromagnetic waves polymerized including (meth) acrylates represented by Formula 1 below. By including a binder resin for shielding, long-term dispersion stability of the conductive filler is improved, and there is an advantage of having excellent ejectability.

[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

Furthermore, the above-described coating composition for electromagnetic wave shielding has excellent dispersion stability for a long period of time and has excellent sprayability, so that a thin film electromagnetic wave shielding film having uniform physical properties can be realized by spraying, and the prepared electromagnetic wave shielding film has heat resistance, It has excellent transparency and cross-cut characteristics, and has the advantage of having a pencil hardness of 4H or more.

1 is a graph showing the dispersion stability index (TSI) of a coating composition for electromagnetic wave shielding according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail through specific examples or examples including the accompanying drawings. However, the following specific examples or examples are only one reference for explaining 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 meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms used in the description in the present invention are merely to effectively describe specific embodiments and are not intended to limit the present invention.

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

In addition, when a certain component is said to "include", this means that it may further include other components without excluding other components unless otherwise stated.

The term '(meth)acrylate' used in the present invention is used in the sense of including both 'methacrylate' and 'acrylate'.

The present invention for achieving the above object provides a binder resin for electromagnetic wave shielding, a coating composition for electromagnetic wave shielding comprising the same, and an electromagnetic wave shielding film prepared therefrom.

The present inventors have recognized the difficulty in forming a shielding film capable of realizing homogeneous electromagnetic wave shielding characteristics due to the poor dispersibility of the conductive filler due to the difference in specific gravity in the conventional coating composition for electromagnetic wave shielding, and a new electromagnetic wave shielding solution to solve this problem. Research on binder resin was intensified.

Accordingly, (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) saturated diacid compound and hydroxy (C2-C4) alkyl (meth) acrylate A binder resin for electromagnetic wave shielding comprising a polymerized binder resin including a monomer prepared by condensation, (d) cyclo(C3-C6)alkyl(meth)acrylate and (e) (meth)acrylate represented by Formula 1 below As it is used as a filler, it is possible to implement uniform dispersion of the conductive filler, and it has excellent dispersion stability and ejectability even after a long period of time, so it has excellent electromagnetic wave shielding performance, heat resistance, transparency, and cross The present invention was completed after confirming that an electromagnetic wave shielding film having excellent cut characteristics and a pencil hardness of 4H or more could be formed.

[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

Hereinafter, a binder resin for electromagnetic wave shielding according to the present invention, a coating composition for electromagnetic wave shielding comprising the same, and an electromagnetic wave shielding film prepared therefrom will be described in detail.

The binder resin for electromagnetic wave shielding of the present invention is (a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) a saturated diacid compound and hydroxy (C2- Polymerization including a monomer prepared by condensation of C4) alkyl (meth) acrylate, (d) cyclo (C3-C6) alkyl (meth) acrylate and (e) (meth) acrylate represented by Formula 1 below It became.

[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ ))

The (a) (C3-C7) alkyl (meth) acrylate (hereinafter referred to as monomer (a)) is propyl methacrylate, propyl acrylate, isobutyl acrylate, isobutyl methacrylate, normal butyl meth acrylate. Normal butyl acrylate, pentyl acrylate, normal hexyl acrylate and their isomers, normal peptyl acrylate and various alkyl (meth) acrylates falling into the above categories, such as isomers thereof, can be exemplified. Among them, normal butyl acrylate is more preferred in order to satisfy various properties desired by the present invention, such as coating property, adhesiveness, surface hardness, and dispersibility, but is not limited thereto.

The (b) (C3-C7) alkyl (meth) acrylate is propyl methacrylate, propyl acrylate, isobutyl acrylate, isobutyl methacrylate, normal butyl methacrylate. Normal butyl acrylate, pentyl acrylate, normal hexyl acrylate and their isomers, normal peptyl acrylate and various alkyl (meth) acrylates falling into the above categories, such as isomers thereof, can be exemplified. Among them, normal butyl acrylate is more preferred in order to satisfy various properties desired by the present invention, such as coating property, adhesiveness, surface hardness, and dispersibility, but is not limited thereto.

The monomer (hereinafter, referred to as monomer (c)) prepared by condensation of the (c) saturated diacid compound and hydroxy (C2-C4) alkyl (meth) acrylate is composed of the saturated diacid compound and the hydroxy (C2-C4) -C4) It may be prepared by dehydration in various ways such as acid or base reaction of alkyl (meth) acrylate. The saturated diacid compound may be, for example, one or more saturated diacids selected from succinic acid, malic acid, adipic acid, glutaric acid, and the like, preferably selected from succinic acid, malic acid, adipic acid, and glutaric acid. Any one or more can be used, and more preferably succinic acid that can achieve the physical properties of the present invention well. The hydroxy (C2-C4) alkyl (meth) acrylate is specifically, 2-hydroxyethyl acrylate, 2-hydroxymethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl It may include acrylate and various isomers thereof, preferably, hydroxyethyl acrylate may be used, but is not limited thereto.

A specific preferred example of the monomer prepared by condensation of the (c) saturated diacid compound and hydroxy (C2-C4) alkyl (meth) acrylate is mono [2- (meth) acryloyloxyethyl] succinate ( Mono-2- (methacryloyloxyethyl) succinate), mono [2- (meth) acryloyloxyethyl] phthalate (Mono-2- (methacryloyloxy) ethyl phthalate), and the like, but is not limited thereto.

The (d) cyclo(C3-C6)alkyl(meth)acrylate (hereinafter, referred to as monomer (d)) is an alicyclic functional group such as cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, etc. as an alicyclic cyclo group. It can be exemplified, but not necessarily limited thereto, and preferably cyclohexyl methacrylate (Cyclohexyl methacrylate) is preferred, but is not limited thereto.

(E) The (meth)acrylate represented by Formula 1 (hereinafter, referred to as monomer (e)) may be prepared by reacting an alkyl (meth)acrylate with a metal chalcogen compound into which a carboxylic acid group is introduced. there is.

[Formula 1]

In Formula 1, M is a metal chalcogen compound, R ₁ is a C2-C6 substituted or unsubstituted alkylene group, and R ₂ is hydrogen or methyl (CH ₃ ).

The metal of the metal chalcogen compound is any one or two or more metals selected from the group consisting of Mo, W, Sn, Bi and Sb, preferably Mo, Sn, and Sb, and the chalcogen of the metal chalcogen compound may be one or two or more elements selected from the group consisting of S, Se and Te, preferably S and Se.

With respect to the entirety of the electromagnetic wave shielding binder resin according to an embodiment of the present invention, the content of the monomer is not limited, but 20 to 35% by weight of the monomer (a), 10 to 20% by weight of the monomer (b), monomer ( c) 20 to 35% by weight, 15 to 25% by weight of monomer (d), 1 to 20% by weight of monomer (e), more preferably 22 to 30% by weight of monomer (a), monomer (b) 13 to 20% by weight, monomer (c) 22 to 30% by weight, monomer (d) 18 to 25% by weight, monomer (e) 10 to 20% by weight, but may be included, but prepared within the above range The binder resin is preferred because it can implement excellent dispersion stability in the coating composition to be described later.

The coating composition for electromagnetic wave shielding of the present invention may include the above-described binder resin for electromagnetic wave shielding, a conductive filler, and a diluent.

The conductive filler may specifically include one or more components selected from metal particles, metal salts, conductive polymers, carbon particles, carbon tubes, carbon nanotubes, graphene, and graphene oxide. The metal may be any one or two or more selected from gold (Au), silver (Ag), platinum (Pt), aluminum (Al), copper (Cu), and alloys thereof, but is not limited thereto. At this time, the shape of the conductive filler may be spherical or irregular powder form, flakes, core-shell particles, etc., but is not limited thereto, and the average particle size may be nanoscale, specifically 1 nm to 10 μm It may be, and more specifically, it may be 100 to 800 nm, but is not limited thereto.

The diluent may be used without limitation as long as it dissolves the binder resin and dissolves the conductive polymer when the conductive filler is a conductive polymer, and is not limited as long as it disperses particles such as the metal particles or carbon particles. Specific examples of the diluent include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, tetrahydrofuran, acetone, ethyl acetate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, benzyl alcohol, and cyclohexane. Any one or a mixture of two or more selected from rice, dichlorobenzene, nitrobenzene, dimethyl sulfoxide, glycerol, propylene glycol methyl ether, Cellusolve, and glycols may be used, but is not limited thereto no.

The coating composition for electromagnetic wave shielding according to an embodiment of the present invention may include 5 to 50% by weight of the electromagnetic wave shielding binder resin, 10 to 70% by weight of the conductive filler, and 20 to 80% by weight of the diluent, preferably. may include 10 to 40% by weight of the electromagnetic wave shielding binder resin, 20 to 65% by weight of the conductive filler, and 25 to 70% by weight of the diluent, but is not limited thereto, and is adjusted to various composition ratios depending on the use Available. In addition, additional additives may be included within a range without deterioration of physical properties, and an example of the additives may include a plasticizer, a defoamer, and the like, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the above-described coating composition. It may include, but is not limited to.

The coating composition for shielding electromagnetic waves according to an embodiment of the present invention includes the above-described binder resin for shielding electromagnetic waves and the conductive filler together, so that excellent dispersion stability can be realized for a long time, and compared to the initial stage of manufacture, the dispersibility of the conductive filler Reduction may be significantly reduced, which may be more desirable. More specifically, the coating composition for electromagnetic wave shielding according to a preferred embodiment of the present invention may have a dispersion stability index (TSI) of less than 3.5 for 45 hours, preferably a dispersion stability index (TSI) of less than 2.5 for 45 hours. , may be better less than 1.5. In addition, the coating composition for electromagnetic wave shielding may have a change rate of dispersion stability index (TSI) of less than 1.5, preferably less than 1.0, and more preferably less than 0.5 after 3.5 hours compared to the initial time. That is, compared to the initial stage, a rapid decrease in dispersion stability is suppressed, and uniform dispersion stability is obtained for a long time, so that an effect excellent in physical properties of the electromagnetic wave shielding film described later can be realized, which is more preferable.

As a preferred embodiment of the present invention, it may include an electromagnetic wave shielding film formed of the above-described coating composition for electromagnetic wave shielding.

The electromagnetic wave shielding film may be formed by applying and drying the above-described coating composition for electromagnetic wave shielding by a known method, and in the present invention, it may be preferably applied by a spray method, 160 ℃ to 230 ℃ It may be drying at ° C, preferably drying at 170 ° C to 200 ° C, but is not limited thereto. Any known method for drying may be used without limitation, and specifically, a drying oven, hot air, or the like may be used.

The electromagnetic wave shielding film may have a thickness of 0.1 μm to 50 μm, specifically, 5 μm to 30 μm, but is not limited thereto.

The electromagnetic wave shielding film may have a pencil hardness of 3H or more, preferably 4H or more. In addition, the electromagnetic wave shielding film may have a cross cut of 4B or more according to ASTM D 3359 standard, and preferably may have a cross cut of 5B or more. In addition, the electromagnetic wave shielding film may have a water contact angle of 50 degrees or more and an electrical conductivity of 60 mΩ/10 μm or less.

As described above, the coating composition including the binder resin for shielding electromagnetic waves according to an embodiment of the present invention has excellent dispersion stability in the initial stage and for a long period of time, so that a coating composition in which a conductive filler is homogeneously dispersed can be implemented, and excellent It has sprayability and is suitable for spray coating, and the electromagnetic wave shielding film manufactured using this has advantages of good adhesion to substrates of various materials, excellent transparency and surface hardness, and realizing uniform electromagnetic wave shielding ability.

The present invention will be described in more detail based on the following Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Test method]

1. Measurement of turbiscan stability index (TSI)

The dispersion stability index over time was measured using TRUBISCAN using the coating composition containing the prepared binder resin.

2. Measurement of contact angle

After coating the prepared binder resin on a glass substrate and drying at 150 ° C. to form a film, water droplets were dropped according to the ASTM D 5946 standard, and the angle formed between the still water droplets and the film surface was measured.

3. Heat resistance measurement

The prepared electromagnetic wave shielding film was cut into a size of 50 mm in diameter, bonded to glass with an acrylic pressure-sensitive adhesive, and changes in transparency were observed according to temperature changes, and evaluated according to the following evaluation criteria.

◎: Totally transparent O: Partially slightly yellowish, △: Partially yellowish, X: Overall yellowish

4. Ejectability measurement

After coating the coating composition containing the prepared binder resin on the Si Wafer using a spray coating equipment, the degree of application was visually observed and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

Good: Applied evenly throughout;

Moderate: Partial agglomeration occurs;

Bad: Clumping occurs overall

5. Adhesion measurement (cross-cut)

After making a scratch by crossing a 10x10 (mm) line on the surface of the manufactured electromagnetic shielding film with a cross hatch cutter, attach the tape, rub it off with a uniform force, and count the pieces of film that have come off the coated surface on the tape. Measured according to the ASTM D3359 standard, the degree of adhesion was expressed as 0B to 5B values.

6. Pencil Hardness Measurement

Based on ASTM D3362, the prepared electromagnetic wave shielding film was measured for pencil hardness under a load condition of 500 g.

[Production Example]

5g of MoS ₂ powder was put into a ball mill cylinder together with a steel ball, and MoS ₂ powder ball milled at 500 rpm for 48 hours in a CO ₂ atmosphere was added with 1M HCl solution, stirred for 48 hours, and dried to prepare MoS ₂ -COOH. did

After mixing 0.5 g of prepared MoS ₂ -COOH, 0.68 ml of HEMA, and 200 ml of DMF, and raising the temperature to 80 ° C in a nitrogen atmosphere, a solution of 0.46 g of DCC and 6.8 mg of DMAP dissolved in 10 ml of DMF was added dropwise at room temperature. Stirred for 24 hours. Thereafter, centrifugation was performed once at 6000 rpm to remove the supernatant, and the sample on the wall was washed with ethanol through a membrane filter, dried in a vacuum oven at 50 ° C for 12 hours, and MoS ₂ - represented by Formula 1-1 g-HEMA was prepared.

[Formula 1-1]

[Example 1]

7 mg of MoS ₂ -g-HEMA prepared in Preparation Example and 58 ml of ethyl acetate were heated to 80 °C while stirring at a speed of 500 rpm using a mechanical stirrer. Then, methyl methacrylate (MMA) 7.0 g, BA 4.5 g, mono (2-acrylolyoxyethyl) Succinate (HEA_suc) 8.0 g, cyclohexyl methacrylate (Cyclohexyl methacrylate , Ca) 5.9 g and AIBN 0.13 g dissolved in ethyl acetate (EAc) were mixed well and added dropwise. In order to additionally remove unreacted monomers, after 2 hours, 0.013 g of 2,2'-azo-bis-isobutyrylnitrile (AIBN) was dissolved in 5 ml EAc and added dropwise, followed by 3 By time reaction, a MoS ₂ -g-HEMA (0.1 wt%) binder resin containing MoS ₂ -g-HEMA at 0.1 wt% based on MMA was prepared. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

[Example 2]

14 mg of MoS ₂ -g-HEMA prepared in Preparation Example and 58 ml of ethyl acetate (Ethyl Acetate, EAc) were stirred at a speed of 500 rpm using a mechanical stirrer and the temperature was raised to 80 °C. Then, methyl methacrylate (MMA) 7.0 g, butyl acrylate (Butyl acrylate, BA) 4.5 g, mono 2-acryloylethyl succinate (Mono (2-acrylolyoxyethyl) Succinate, HEA_suc) 8.0 g, Cyclohexyl methacrylate (Ca) 5.9g (please define exactly which cycloalklyacrylate it is) and 2,2'-azo-bis-isobutylnitrile (2,2'-azo-bis -isobutyrylnitrile, AIBN) 0.13 g was added dropwise after mixing well. In order to additionally remove unreacted monomers, 0.013 g of AIBN was dissolved in 5 ml EAc dropwise after 2 hours and reacted for 3 hours to obtain MoS ₂ -g- containing MoS ₂ -g-HEMA at 0.1% by weight relative to MMA. A HEMA (0.2 wt%) binder resin was prepared. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

[Example 3]

21 mg of MoS ₂ -g-HEMA prepared in Preparation Example and 58 ml of ethyl acetate (Ethyl Acetate, EAc) were stirred at a speed of 500 rpm using a mechanical stirrer and the temperature was raised to 80 °C. Then, methyl methacrylate (MMA) 7.0 g, butyl acrylate (Butyl acrylate, BA) 4.5 g, mono 2-acryloylethyl succinate (Mono (2-acrylolyoxyethyl) Succinate, HEA_suc) 8.0 g, 5.9 g of cyclohexyl methacrylate (Ca) and 0.13 g of 2,2'-azo-bis-isobutyrylnitrile (AIBN) dissolved in EAc were mixed well and added dropwise. did In order to additionally remove unreacted monomers, 0.013 g of AIBN was dissolved in 5 ml EAc dropwise after 2 hours and reacted for 3 hours to obtain MoS ₂ -g- containing MoS ₂ -g-HEMA at 0.1% by weight relative to MMA. A HEMA (0.3 wt%) binder resin was prepared. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

[Example 4]

28 mg of MoS2-g-HEMA prepared in Preparation Example and 58 ml of ethyl acetate (Ethyl Acetate, EAc) were heated to 80 °C while stirring at a speed of 500 rpm using a mechanical stirrer. Then, methyl methacrylate (MMA) 7.0 g, butyl acrylate (Butyl acrylate, BA) 4.5 g, mono 2-acryloylethyl succinate (Mono (2-acrylolyoxyethyl) Succinate, HEA_suc) 8.0 g, 5.9 g of cyclohexyl methacrylate (Ca) and 0.13 g of 2,2'-azo-bis-isobutyrylnitrile (AIBN) dissolved in EAc were mixed well and added dropwise. did In order to additionally remove unreacted monomers, 0.013 g of AIBN was dissolved in 5 ml EAc dropwise after 2 hours and reacted for 3 hours to obtain MoS ₂ -g- containing MoS ₂ -g-HEMA at 0.1% by weight relative to MMA. A HEMA (0.4 wt%) binder resin was prepared. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

[Example 5]

35 mg of MoS ₂ -g-HEMA prepared in Preparation Example and 58 ml of ethyl acetate (Ethyl Acetate, EAc) were heated to 80 °C while stirring at a speed of 500 rpm using a mechanical stirrer. Then, methyl methacrylate (MMA) 7.0 g, butyl acrylate (Butyl acrylate, BA) 4.5 g, mono 2-acryloylethyl succinate (Mono (2-acrylolyoxyethyl) Succinate, HEA_suc) 8.0 g, 5.9 g of cyclohexyl methacrylate (Ca) and 0.13 g of 2,2'-azo-bis-isobutyrylnitrile (AIBN) dissolved in EAc were mixed well and added dropwise. did In order to additionally remove unreacted monomers, 0.013 g of AIBN was dissolved in 5 ml EAc dropwise after 2 hours and reacted for 3 hours to obtain MoS ₂ -g- containing MoS ₂ -g-HEMA at 0.1% by weight relative to MMA. A HEMA (0.5 wt%) binder resin was prepared. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

[Comparative Example 1]

Example 1 was carried out in the same manner as in Example 1, except for preparing without using MoS ₂ -g-HEMA. The thermal properties, molecular weight and molecular weight distribution of the prepared polymers are listed in Table 1.

T _d5 (Unit: ℃) T _g (Unit: ℃) Mn (unit: g/mol) Mw (unit: g/mol) PDI Example 1 260.17 43.35 72,600 124,000 1.71 Example 2 254.48 23.48 81,100 144,000 1.77 Example 3 240.81 33.37 74,700 124,000 1.66 Example 4 255.85 39.42 79,300 123,000 1.56 Example 5 264.00 32.13 47,900 104,000 2.17 Comparative Example 1 263.86 41.27 93,100 171,000 1.83

Using the binder resin prepared in the above Examples and Comparative Example 1, a coating composition having the composition shown in Table 2 below was prepared.

12% by weight of the binder prepared in the above Examples and Comparative Example 1, 45% by weight of a conductive filler (HP-0708 from LT Metal), 38% by weight of propylene glycol monomethyl ether as a diluent, and a defoaming agent as an additive (BYK's BYK-054) was mixed at 5% by weight to prepare coating compositions as shown in Table 2 below, respectively, and sprayability and dispersion stability were evaluated.

type Example 6 Example 7 Example 8 Example 9 Comparative Example 2 Binder resin/content (unit: parts by weight) Example 2 /
12 Example 3 /
12 Example 4 /
12 Example 5 /
12 Comparative Example 1 /
12 Conductive filler (LT Metal's HP-0708.)
(unit: parts by weight) 45 45 45 45 45 Diluent (Propylene glycol monomethyl ether)
(unit: parts by weight) 38 38 38 38 38 Additive (BYK-054)
(unit: parts by weight) 5 5 5 5 5 Ejectability good good good good good Dispersion stability
(TSI) 3.5h 1.25 0.825 0.126 0.125 1.5 42h 2.25 1.75 1.125 1.0 3.25

As shown in Table 2 and FIG. 1, in the case of Examples 6 to 9, which are coating compositions according to the present invention, dispersion stability during 3.5 hours from the beginning of preparation is not only significantly better than that of Comparative Example 2, but in particular, Examples In the case of 9 and 10, compared to Comparative Example 2, the overall dispersion stability is far superior, and it can be seen that the dispersion stability index (TSI) is maintained uniformly at a low value without a significant change in dispersion stability for 42 hours.

Measurement of physical properties of electromagnetic wave shielding film

The coating compositions of Examples and Comparative Example 2 having the compositions of Table 2 were spray-coated on a silicon substrate, and the coating was dried to prepare an electromagnetic wave shielding film. Heat resistance, adhesiveness, and pencil strength of the prepared electromagnetic wave shielding film were measured and shown in Table 3 below.

coating composition
type heat resistance Cross-cut contact angle
(unit) pencil
Hardness 120℃, 30min 150℃, 30min 180℃, 30min 260℃,
1h Example 6 ◎ ◎ O X 5B 53.69 4H Example 7 ◎ ◎ O X 5B 56.85 4H Example 8 ◎ ◎ O X 4B 58.65 4H Example 9 ◎ ◎ △ X 5B 64.97 4H Comparative Example 2 ◎ O O △ 4B 41.37 2H

As shown in Table 3, it can be seen that the electromagnetic wave shielding films of Examples 6 to 9 using the coating composition according to the present invention have excellent heat resistance and excellent adhesion of 4B or more and excellent pencil hardness of 4H or more.

As described above, the present invention has been described by specific details and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (13)

(a) methyl methacrylate (MMA), (b) (C3-C7) alkyl (meth) acrylate, (c) by condensation of a saturated divalent acid compound and hydroxy (C2-C4) alkyl (meth) acrylate The prepared monomer, (d) cyclo (C3-C6) alkyl (meth) acrylate and (e) (meth) acrylate represented by the following formula (1) polymerized by including a binder resin for electromagnetic wave shielding.
[Formula 1]

(In Formula 1, M is a metal chalcogen compound, R ₁ is a C2~C6 substituted or unsubstituted alkylene group, R ₂ is hydrogen or methyl (CH ₃ )) According to claim 1,
The metal of the metal chalcogen compound is any one or two or more metals selected from the group consisting of Mo, W, Sn, Bi and Sb, and the chalcogen of the metal chalcogen compound is any one selected from the group consisting of S, Se and Te. Binder resin, which is one or two or more elements. According to claim 1,
The saturated diacid compound is any one or more selected from succinic acid, malic acid, adipic acid, and glutaric acid. A coating composition for shielding electromagnetic waves comprising the binder resin for shielding electromagnetic waves according to any one of claims 1 to 3, a conductive filler, and a diluent. According to claim 4,
The conductive filler is a coating composition for electromagnetic wave shielding comprising at least one component selected from metal particles, metal salts, conductive polymers, carbon particles, carbon tubes, carbon nanotubes, graphene, and graphene oxide. According to claim 4,
The composition is a coating composition for electromagnetic wave shielding comprising 10 to 70% by weight of the conductive filler, 5 to 50% by weight of the binder resin for electromagnetic wave shielding, and 20 to 80% by weight of a diluent. According to claim 4,
The coating composition for electromagnetic wave shielding has a dispersion stability index (TSI) of less than 3.5 for 45 hours. According to claim 4,
The coating composition for shielding electromagnetic waves has a change rate of dispersion stability index (TSI) of less than 1.5 after 3.5 hours compared to the initial period. An electromagnetic wave shielding film comprising the binder resin for electromagnetic wave shielding of any one of claims 1 to 3. According to claim 9,
The electromagnetic wave shielding film has a pencil hardness of 3H or more. According to claim 9,
The electromagnetic wave shielding film has a crosscut of 4B or higher according to the ISO 2409 standard. According to claim 9,
The electromagnetic wave shielding film has a water contact angle of 50 degrees or more. According to claim 9,
The electromagnetic wave shielding film has an electrical conductivity of 60 mΩ/10 μm or less.

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